Historically, classical cross-coupling reactions have been a linchpin in synthetic chemistry, enabling the straightforward construction of C(sp 2 )-C(sp ) bonds and thereby propelling the production of planar, biaryl structures. This entrenched reliance on cross-coupling has inadvertently sculpted a discernible bias in small molecule drug design, steering the generation of libraries that predominantly feature structurally analogous, two-dimensional compounds. While there have been laudable strides made within the domain of C(sp )-C(sp 3 ) cross-coupling, contemporary methodologies are oftentimes plagued by several pragmatic limitations. They typically necessitate sizable excesses of one coupling partner and frequently hinge upon non-abundant starting materials, such as air-and moisture-sensitive alkyl organometallics, thereby constraining the reaction scope and practicality in a drug discovery context. Consequently, the quest for alternative strategies that circumvent these limitations while facilitating the construction of three-dimensional molecular structures persists as an imperative in medicinal chemistry research. In recent years, nickel-mediated cross-electrophile (XEC) coupling has emerged as a potent strategy for constructing C(sp 3 )-C(sp 3 ) bonds, utilizing various native and bench-stable aliphatic coupling entities, thus circumventing the use of moisture-sensitive organometallic species. Despite substantial strides within this sphere, exploiting varied, ubiquitous functional groups such as aldehydes as coupling partners has lingered in a state of underdevelopment. Traditionally, aldehydes have been harnessed as carbonyl electrophiles with Mg or Li-based organometallic species or within Nozaki-Hiyama-Kishi (NHK) type reactivity to yield alcohols, yet their employment to forge C(sp 3 )-C(sp 3 ) bonds via a reductive deoxygenative pathway remains, to our knowledge, uncharted. A pioneering approach, that enables the direct coupling of sp 2 and sp 3 electrophiles, such as aldehydes and carboxylic acids, heralds an unprecedented disconnection in the cross-electrophile coupling domain (Figure ). Aryl sulfonyl hydrazones are considered as a bench-stable, activated form of aldehydes due to their known propensity to undergo both radical and polar addition, ultimately yielding deoxygenated, cross-coupled products upon thermal decomposition of alkylated hydrazide intermediates (Figure ). Utilizing abundant aliphatic carboxylic acids activated as NHPI-based redox-active esters (RAEs) to serve as sp electrophiles, and employing visible light-mediated decarboxylation to yield carbon-centered radicals, we envisioned a trapping mechanism with aldehyde sulfonyl hydrazones to, upon sulfinate and dinitrogen extrusion, afford the coveted product (Figure ). In this study, we realise such a metal-free cross-electrophile coupling, leveraging Eosin Y as an economical organophotocatalyst under visible light irradiation. Illustrating the potential of our synthetic strategy becomes particularly appealing when reflecting upon the strategic C1 homologation of carboxylic acids, traditionally achieved through the Arndt-Eistert reaction. Although this protocol, developed in the 1950s, bears chemical reliability, significant limitations persist, particularly those pertaining to the generation, purification, and utilization of toxic and explosive diazomethane, hindering its widespread adoption and applicability. While flow technology has provided a partial answer to these safety challenges, a truly general and practical alternative for such transformation has been elusive. Indeed, polar variants such as the Kowalsky Ester homologation suffer from the use of organolithium bases, strongly limiting the substrate scope of the transformation and its scalability. For seminal radical variants, Barton proposed a photoinduced C1 homologation of N-hydroxy-2-thiopyridone esters, although this strategy suffered from low functional group compatibility, a narrow scope, and requisite lengthy synthetic sequences. In this context, we present the utilization of ethyl glyoxalate-derived sulfonyl hydrazone 2a as a bench-stable and easy-to-handle crystalline radical acceptor to realize the C1 homologation of carboxylic acids under mild conditions (Figure ). As a subsequent, potent application of this synthetic paradigm, our attention was drawn by the synthesis of β-arylethylamines, a prevalent structural motif within numerous drugs and natural products. Although various synthetic routes have been delineated, an intuitive retrosynthetic strategy entailing a cross-coupling reaction between a benzyl electrophile and α-amino nucleophile has remained underrepresented. We posit that the advanced cross-electrophile coupling between NHPI esters and aldehyde sulfonyl hydrazones will provide a straightforward and direct route for the efficient preparation of substituted cyclic and acyclic β-arylethylamines (Figure ).