Photochemical vapor deposition in the optical near field was employed to fabricate nanometric Zn dots on a sapphire substrate. A nonadiabatic photochemical process was used to excite molecular vibrational states in optically inactive zinc-bis(acetylacetonate) (Zn(acac)₂) vapor. Dependence of the deposition rate on the separation distance, d, between the apex of the fiber probe and the substrate was investigated. At d > 5 nm, the dissociation rates of Zn(acac)₂ decreased with increasing d due to the transition probability of ground-state Zn(acac)₂ to excited vibrational states induced by the nonadiabatic photochemical process. At d < 5 nm, the deposition rate decreased with decreasing d, which was attributable to an insufficient supply of gaseous Zn(acac)₂ molecules in the gap space between the fiber probe and the substrate.