DEPT135 was used to study the hydroxymethylation of p-cresol in basic condition. The roles of type and amount of catalyst, reaction temperature, reaction time were investigated to optimize reaction conditions for the synthesis of 2,6-dihydroxymethyl-4-methyl phenol(2,6-DHMMP). Subsequently, a series of novolac resins with extremely high or low M_W, narrow M_W/M_N, as well as alternating co-condensation structure have been produced by the condensation of 2,6-DHMMP and phenol, m-cresol etc. The synthesized p-cresol/phenol resin has a M_W of 20000-30000, and M_W/M_N of 15-20, and also excellent resistance to alcohol and alkali, which meet the needs of photosensitive compositions. The synthesized p-/m-cresol resin has a M_W of 25000, and M_W/M_N of below 15, as well as well resistance to alkali, heat and etching. These novolac resins have good prospects in terms of resist and printing plates.