The matrix isolation technique has been employed to investigate the reaction of OVCl3 with CH3OH. Using twin jet deposition, the initial intermediate in the mechanism was identified as a weakly bound molecular complex. This species is characterized by perturbations to the C-O, V=O, and V-Cl stretching modes. Merged jet deposition, with a room-temperature reaction zone, led to complete conversion to Cl2V(O)OCH3, the second intermediate in the reaction sequence, through HCl elimination from the initial complex. This species was identified by use of extensive isotopic labeling, the observation of HCl as an additional reaction product, and by comparison to density functional calculations. All of the fundamental vibrational modes of this species that lie above 400 cm(-1) were observed, some with very high intensities. Heating the reaction zone above 150 degrees C led to destruction of this intermediate, and production of both CH2O and CH3Cl.