Direct N-allylation of azoles with hydrogen evolution has been achieved through the synergistic combination of organic photocatalysis and cobalt catalysis. The protocol bypasses stoichiometric oxidants and prefunctionalization of alkenes and produces hydrogen (H2) as the byproduct. This transformation highlights high step- and atom-economy, high efficiency, and broad functional group tolerance for further derivatization, which opens a door for C-N bond formation that is valuable in heterocyclic chemistry.