Abstract The catalyst‐free electrochemical halogenation and trifluoromethylation of 4 H ‐pyrido[1,2‐ a ]pyrimidin‐4‐ones was realized under external‐oxidant‐free conditions. This strategy provides an easy and green access to functionalized new 4 H ‐pyrido[1,2‐ a ]pyrimidin‐4‐one derivatives with broad scope, good functional group tolerance and high regioselectivity.