The article by David A. Nicewicz and David W. C. MacMillan describes a novel approach to enantioselective α-alkylation of aldehydes using a combination of photoredox catalysis and organocatalysis. The authors merged these two powerful fields to address long-standing challenges in asymmetric chemical synthesis. Specifically, they used the photoredox catalyst Ru(bpy)3Cl2 and an imidazolidinone organocatalyst to generate an electron-rich enamine and an electron-deficient alkyl radical, respectively. This interwoven activation pathway enabled the direct and highly enantioselective coupling of aldehydes with α-bromo ketones or esters. The mechanism involves the formation of an enamine from the condensation of an aldehyde and the organocatalyst, followed by the addition of this enamine to the alkyl radical, leading to the desired α-alkyl aldehyde product. The study demonstrates the versatility and efficiency of this dual-catalysis approach, which does not require heating or cooling and can be performed using a simple household fluorescent light source. Control experiments and luminescence quenching studies further validate the proposed mechanism, confirming the participation of the *Ru(bpy)3 2+* excited state in the catalytic cycle.The article by David A. Nicewicz and David W. C. MacMillan describes a novel approach to enantioselective α-alkylation of aldehydes using a combination of photoredox catalysis and organocatalysis. The authors merged these two powerful fields to address long-standing challenges in asymmetric chemical synthesis. Specifically, they used the photoredox catalyst Ru(bpy)3Cl2 and an imidazolidinone organocatalyst to generate an electron-rich enamine and an electron-deficient alkyl radical, respectively. This interwoven activation pathway enabled the direct and highly enantioselective coupling of aldehydes with α-bromo ketones or esters. The mechanism involves the formation of an enamine from the condensation of an aldehyde and the organocatalyst, followed by the addition of this enamine to the alkyl radical, leading to the desired α-alkyl aldehyde product. The study demonstrates the versatility and efficiency of this dual-catalysis approach, which does not require heating or cooling and can be performed using a simple household fluorescent light source. Control experiments and luminescence quenching studies further validate the proposed mechanism, confirming the participation of the *Ru(bpy)3 2+* excited state in the catalytic cycle.