HIGHLIGHTS• The introduction of hydroiodic acid (HI) manipulates the dynamic conversion of PbI 2 into highly coordinated species to optimize the nucleation and growth kinetics.• The addition of HI enables the fabrication of CsPbI 3 perovskite quantum dots with reduced defect density, enhanced crystallinity, higher phase purity, and near-unity photoluminescence quantum yield.• The efficiency of CsPbI 3 perovskite quantum dot solar cells was enhanced from 14.07% to 15.72% together with enhanced storage stability.