Methoxy (CH3O-) and deuterated (d-) methoxy (CD3O-) species on Ni(111) are investigated by sum-frequency generation (SFG) spectroscopy. Methoxy adsorbed on the Ni(111) surface is confirmed by SFG spectroscopy to be oriented normal to the surface. Two resonant peaks produced by methoxy, at 2921 and 2821 cm(-1), are assigned to Fermi resonance between the CH symmetric stretching and overtone modes. Deuterated methoxy exhibits a single strong peak at 2051 cm(-1) assigned to the CD symmetric stretching mode. Investigation of the sub-nanosecond transient behavior of methoxy and d- methoxy species on Ni(111) under short-pulse laser pumping at 1064 nm reveals a clear weakening and recovery of the SFG peaks upon heating. The observed temporal profile is reproduced by simulation assuming that the original methoxy in the ground state is in chemical equilibrium with a new state produced by instantaneous heating. The dependence of the SFG spectra on the initial substrate temperature is also reproduced by the simulation. The simulation suggests a temperature jump of 250 K upon laser pumping, inducing a change in the molecular orientation or adsorption site of methoxy on the Ni(111) surface without decomposition of methoxy to adsorbed CO and hydrogen, which occurs under normal heating at 200 K.