The impact of mode-specific vibrational excitations on initial-preparation conditions was studied by examining the excited-state population decay rates in the nonadiabatic dynamics of methyl nitrate (CH3ONO2). In particular, exciting a few specific modes by adding a single quantum of energy clearly decelerated the nonadiabatic dynamics population decay rates. The underlying reason for this slower population decay was explained by analyzing the profiles of the excited-state potential energy surfaces in the Franck–Condon regions and the topology of the S1/S0 conical intersection. This study not only provides physical insights into the key mechanisms controlling nonadiabatic dynamics but also shows the possibility of controlling nonadiabatic dynamics via mode-specific vibrational excitations.