Pyridine motifs are widespread pharmacophores in many drugs. Installing various substituents through pyridine C-H bond functionalization is significant for new drug design and discovery. Developments of late-stage functionalization reactions enrich the strategies for selective functionalization of pyridines. However, late-stage C-H carboxylation of pyridines is a long-standing challenge, especially selectively carboxylation with CO2 on pyridine motifs. Herein, we describe a practical method for C4-H carboxylation of pyridines via one-pot C-H phosphination and copper-catalyzed carboxylation of the resulted phosphonium salts with CO2 . The reaction is conducted under mild conditions and compatible with multiple active groups and several pyridine drugs, providing diverse valuable isonicotinic acid compounds, demonstrating the application potential of this strategy.