Customized Photoelectrochemical C−N and C−P Bond Formation Enabled by Tailored Deposition on Photoanodes

Abstract Photoelectrochemistry (PEC) is burgeoning as an innovative solution to organic synthesis. However, the current PEC systems suffer from limited reaction types and unsatisfactory performances. Herein, we employ efficient BiVO 4 photoanodes with tailored deposition layers for customizing two PEC approaches toward C−N and C−P bond formation. Our process proceeds under mild reaction conditions, deploying easily available substrates and ultra‐low potentials. Beyond photocatalysis and electrocatalysis, customized PEC offers high efficiency, good functional group tolerance, and substantial applicability for decorating drug molecules, highlighting its promising potential to enrich the synthetic toolbox for broader organic chemistry of practical applications.