The synthetic routes of many biologically active molecules have been dominated by the use of C(sp 2 )-C(sp 2 ) cross-coupling reactions, resulting in a significant bias towards flat molecules. To improve the probability of finding new potent drugs and agrochemicals, a new trend has emerged to increase the sp -character of new leads (so-called Escape-from-Flatland strategy). Consequently, there is a pressing need to develop new synthetic strategies that can realize the creation of C(sp )-C(sp ) bonds. Historically, alkyl-alkyl couplings have been challenging to accomplish, but in recent years significant progress has been achieved using transition-metal catalysis, particularly by exploiting nickel-based complexes. These methods rely on the availability of prefunctionalized electrophiles (e.g., alkyl halides) and nucleophilic coupling partners (i.e., organometallic reagents), and often require high catalyst loadings, which necessitate energyintensive purification strategies to remove any trace metal impurities. Alternatively, an attractive option to enable C(sp 3 )-C(sp ) bond formation would be to use easily accessible reagents in the absence of any transition metals, which would also facilitate applications that require higher regulatory scrutiny, such as the late-stage functionalization of medicinally relevant compounds. To realize this synthetic goal, we were drawn to Nsulfonyl hydrazones, which are stable, crystalline compounds and are readily synthesized from the corresponding aldehydes (Figure ). Notably, these N-sulfonyl hydrazones can be exploited as a suitable electrophilic site for both polar and radical addition to yield, upon dinitrogen and sulfinate extrusion, the targeted C(sp 3 )-C(sp 3 ) bonds. To realize a metalfree protocol, we anticipated that a photocatalytic Hydrogen Atom Transfer (HAT) strategy would be appealing to activate aliphatic C-H bonds, thus generating from cheap commodity chemicals the required nucleophilic radicals which can subsequently add to the polarity-matched N-sulfonyl hydrazone. Herein, we describe the realization of such a photocatalytic deoxygenative alkylation of N-sulfonyl hydrazones using diarylketones as the photocatalyst (Figure ). Furthermore, the use of glyoxylate-derived sulfonyl hydrazones enables the formal α-alkylation of esters using cheap aliphatic scaffolds as radical precursors (Figure ). It should be noted that these compounds cannot be prepared from common silyl ketene acetals as radical acceptors due to the polarity mismatch between the electron-rich alkene and the nucleophilic alkyl radical (Figure ). Finally, we show that the application of this chemistry provides a preparatively useful route to various medicinally-relevant compounds, such as homobenzylic ethers, aryl ethyl amines, β-amino acids and other moieties which are commonly encountered in approved pharmaceuticals and natural products (Figure ). Our experimental investigation began with the optimization of the photocatalytic HAT step.