AbstractIn the photolysis of diazomethane‐methanol. mixture, the reaction of methylene with methanol gives dimethyl ether and ethanol as products. The ratio of dimethyl ether to ethanol is found to be independent to pressure and to. the composition of diazomethane‐methanol mixture. Methylene insertion into O—H bond is about 11 times faster than that into C—H bonds of methanol. The ratio decreases with increase of temperature.In the diazomethane‐ethanol system, ethylmethyl ether, propanol‐1 and propanol‐2 are found as the products of insertion reaction of methylene into ethanol. The ratios of ethylmethyl ether to propanol‐1 and to propanol‐2 are both found to be almost constant and independent to pressure and to the composition of diazomethane‐ethanol mixture. A small temperature effect on the ratios are observed. The rate of insertion of methylene into O—H bond is about 7.3 and 14.2 times faster than those into primary and secondary C—H bonds o