Tetra-4-pyridylmethane (1), a useful tetrahedral bridging ligand molecule, was effectively obtained by the pyrolysis of tri(4-pyridyl)-4-pyridylazomethane, which was easily prepared from tri-4-pyridylmethane (2) in one step. The overall yield was 32%, which was about 10 times higher than the first reported synthesis (3% from 2).