In this work, sulfobetaine (4-(trialkylammonium) propansultan (TAAPS)) was first developed as a new phase-transfer catalyst for synthesizing dialkoxymethane. The addition reaction of 1,3-propane sultone (PS) and trialkylamines (TAA) was successfully carried out to synthesize sulfobetaines in a homogeneous organic solution. In this work, for the first time, five different TAAPSs, which possess high reactivity, stability, selectivity, and performance, were employed as phase-transfer catalysis to synthesize dialkoxymethane. The reaction of alcohol and dibromomethane in a highly alkaline solution of KOH/organic solvent two-phase medium to produce dialkoxymethane was carried out under phase-transfer catalysis using 4-( trialkylammonium) propansultan as the catalyst. From the experimental observation, a rational reaction mechanism using this new phase-transfer catalyst was proposed. Kinetics of the reaction are studied in detail.