Some new substituted 1,8‐ naphthyridines 2a, 2b, 2c, 2d, 2e, 2f, 2g have been synthesized by treating various 2‐substituted vinamidinium salts 1a, 1b, 1c, 1d, 1e, 1f, 1g with 2,6‐diaminopyridine. The structures of the synthesized compounds have been established on the basis of elemental analysis and spectroscopic data (1H‐NMR, 13C‐NMR, IR, UV/VIS, and mass).