Broad-band, W-visible light irradiation of matrices formed by co-condensation of Li atomic vapor (0.01-0.2 mol % Li) with argon containing N2O and CH4 results in production of methanol at rates which are much greater than the corresponding process with no Li present, as measured by FTIR spectroscopy. The threshold wavelength for methanol production is observed to change from about 220 nm, with no alkali metal present, to between 350 and 400 nm with Li present. The rate of growth of methanol, in irradiation time, is linearly related to the rate of depletion of N2O, indicating that methanol formation is associated with production of a reactive form of atomic oxygen during N2O decomposition. The rate of methanol production is strongly dependent on the concentration of N2O, reaching a maximum at 0.4% N2O, above and below which the rate decreases. The primary reaction is interpreted as an electron transfer from Li to N2O, initially within a weakly interacting, Li-N2O complex which is observed spectroscopically at the time of sample formation. This transfer is believed to form N2O-, which decomposes to form O- initially. O-, or O(D-1) formed from o(-) following a photodetachment process, then formally inserts into the C-H bond of methane to yield methanol. Regeneration of Li atoms via electron transfer from product anions or O- to Li+ is proposed to account for the high yield of methanol formed. Extended irradiation generates the known formaldehyde-water complex, due to O(D-1) or O- reaction with methanol.