A CO2 TEA laser has been used to initiate the collisionless multiphotondissociation of CH3OH between 1000 and 10 mtorr. The appearance of OH(X2Πi) 50±20 nsec after the laser pulse, independent of initial CH3OH pressure (50–200 mtorr), suggests the primary dissociative channel CH3OH+n hν→CH3 +OH(X2Πi); although CH3 could not be correspondingly confirmed. The appearance of CH(X2Πr) 70±20 nsec after the OH(X) appearance, independent of initial CH3OH pressure (70–400 mtorr), suggests secondary collisionless dissociation. Initial rovibronic distributions of OH(X) and CH(X) were determined, as well as characteristic decay time constants. The observation of the relaxation of OH(X) over a 10 μsec time interval after radical onset, allowed the separate characterization of collisional rotational relaxation and translational diffusion.