β-chloroacylation of alkenes using the well-known Friedel-Crafts acylation generally leads to the formation of α,β-unsaturated ketones due to the instability of β-chloroketones under acidic conditions (Fig. ). Thus, the thermal reaction modes to access β-chloroketones are limited to BiCl3catalyzed chlorination of β-silyloxy ketones using TMSCl and SiCl4/PhOHpromoted hydrochlorination of α,β-unsaturated ketones. In 2019, the Ngai group developed the proton-coupled electron-transfer (PCET)-mediated chloroacylation of alkenes from aroyl chlorides (E red = -1.26 V vs SCE for benzoyl chloride) using fac-Ir(ppy)3 [E red 1/2*(*Ir 3+ /Ir 4+ ) = -1.73 V vs SCE] for the synthesis of α,β-unsaturated ketones where 2,6-di-t-butyl-4-methylpyridine was used to form the corresponding *Py-HCl as a PCET catalyst (Fig. ). While this work formally constitutes the photolytic Friedel-Crafts acylation of alkenes, the isolation of β-chloroketones was only achieved for two substrates after a reverse phase HPLC purification. Recently, the visiblelight mediated intermolecular β-chloroacylation of styrenes and α-CF3 substituted styrenes has been reported separately by Oh et al. and Liu et al. using fac-Ir(ppy)3 as the photocatalyst (Fig. ). While these strategies have been successful for the 1,2-chloroacylation of styrenes, its translation to unactivated alkenes has proved elusive. The Xu group's and Ngai group's findings on the addition of acyl radical species to alkenes under photolytic conditions using Ir-photocatalyst have led to the formation of fused pyran 28 and 3,3-dialkyl 2-oxindole derivatives and functionalized 1,4-, 1,6-, and 1,7diketones in an intramolecular fashion without chlorine incorporation. Additionally, the photoactivation of aroyl chlorides using a combination of Cu(I) catalyst and rac-BINAP as ligand was reported by the Ngai group for the synthesis of different heterocycles and carbocycles via intramolecular radical cyclization following the addition of acyl radicals to alkenes with no chlorine incorporation (Fig. ). In contrast, the Xu group reported aroylchlorination of 1,6-dienes via acyl radical addition to activated acrylamides followed by intramolecular atom transfer radical cyclization process using Ir(ppy)3 as the photocatalyst, which allowed the incorporation of a chlorine atom into the products (Fig. ). Despite the exceptional progress achieved, this type of transformation still needs to be revised to avoid prominent restrictions such as limited substrate scope and use of precious Ir-photocatalyst. Nonetheless, the 1,2-chloroacylation of all kinds of alkenes would produce molecules with greater threedimensionality, thus offering a larger accessible chemical space that can be leveraged in pharmaceutical research. From previous reports, it can be concluded that the challenges associated with developing such a photocatalytic method are primarily due to the instability of the generated alkyl radical intermediate II unless it is a benzylic (Fig. , case of styrenes) or tertiary radical species. Further, successful implementation of such methods using acid sensitive Ir-photocatalysts is hampered due to the necessity to employ a base, resulting in the competitive deprotonation of the carbocation intermediate III (Fig. ). A Cu(I)-promoted photocatalytic ATRA platform has the potential to avoid the formation of cation III via an innersphere radical rebound mechanism initiated by a radical capture generating transient Cu(III)-complex IV that could forge the C-Cl bond through a reductive elimination (Fig. ). However, such reactions have not been reported using the well-known Cu(I)-phenanthroline complexes despite having reduction potentials (ECu(II)/Cu(I)* = -1.43 V vs SCE for [Cu(dap)2]Cl and ECu(II)/Cu(I)* = -1.54 V vs SCE for [Cu(dmp)2]Cl) that are sufficient to reduce aroyl chlorides. This may be a consequence of the very short excited-state lifetimes (90 ns to 270 ns) of homoleptic Cu(I)-phenanthroline complexes to execute single electron reduction of aroyl chlorides. We posited heteroleptic Cu(I)-complexes could emerge as a selective and sustainable alternative owing to their longer excited-state lifetimes, enabling them to facilitate single electron manifolds specifically for the Csp2-X molecules such as aroyl chlorides.