Metallaphotocatalysis often needs light-absorbing metal-polypyridyl complexes, semiconductors, or organic dyes, which can modify the oxidation state of metal catalysts. Here, we first report that photoexcitation of Hantzsch ester can directly activate chromium reagents through a single-electron transfer process. The synthetic application was demonstrated through a photoredox decarboxylative allylation of aldehydes with feedstock butadiene without exogenous photocatalysts, metallic reductants, or additives.