Coordination bonding has been employed for the first time to control molecular orientation in thin films and is demonstrated by using tetrapyridylporphyrin. Changing the central metal ion of porphyrin controls the balance of the coordination bonding and hydrogen bonding, and edge-on orientation has been realized for the first time as well as face-on orientation. The mechanism of the film structure formation is comprehensively explained based on the electron configuration of the central metal ion.