Dual palladium/photoredox-catalysis provides an effective method for the decarboxylative asymmetric synthesis of vicinal α,β-tri/tetra- or α,β-tetrasubstituted homoallylic alcohols using Hantzsch-type esters as radical precursors. This mild methodology capitalizes on vinyl cyclic carbonates as accessible reagents providing the target molecules in appreciable to good yields, high branch selectivity, and enantiomeric ratios of up to 94:6, making it a rare example of using prochiral electrophiles for the creation of vicinal congested carbon centers.