The use of electricity over traditional stoichiometric oxidants is a promising strategy for sustainable molecular assembly. Herein, we describe the rhoda‐electrocatalyzed C−H activation/alkylation of several N‐heteroarenes. This catalytic approach has been successfully applied to several arenes, including biologically relevant purines, diazepam, and amino acids. The versatile C−H alkylation featured water as a co‐solvent and user‐friendly trifluoroborates as alkylating agents. Finally, the rhoda‐electrocatalysis with unsaturated organotrifluoroborates proceeded by paired electrolysis.