This work reports the first photochemical Nozaki-Hiyama-Kishi coupling enabled by bioinspired Hantzsch ester. The salient feature of this process is that commercially available and low-cost organic photoactive Hantzsch ester can serve as both an electron and a proton donor to reduce Cr/Ni to low-valent species and hydrolyze the Cr III -alkoxy bond, thus bypassing the use of stoichiometric metallic reductants and additives such as TMSCl and Cp 2 ZrCl 2 . The mild conditions and operationally easy method showed broad compatibility with various alkenyl triflates and aldehydes, including electron-poor pentafluorobenzaldehyde which failed under previous conditions.