Catalytic performance of various acids in the coupling reaction of formaldehyde and methyl formate to produce methyl glycolate and methyl methoxy acetate has been studied. The influence of reaction conditions, such as catalyst amount, reaction temperature, reaction time, and molar ratio of formaldehyde to methyl formate, has also been investigated. The results showed that the acid strength had great influence on the reaction, namely, stronger acids had higher activities. It was also found that the reaction temperature and time had significant effect on the reaction, and the preferable conditions were quite different as different acids were used.