N‐Arylation of N‐containing heterocycles, such as pyrazoles, imidazoles, and benzimidazoles with aryl‐, heteroaryl‐, and vinylboronicacids was efficiently carried out by copperfluorapatite (CuFAP) catalyst in MeOH at room temperature under base‐free conditions. The N‐arylated heterocycles were isolated in good‐to‐excellent yields.