Alkylation of 1,3,5-trihydroxy-2,4,6-trinitrobenzene (TNPG) is a key reaction to the synthesis of 2,4,6trinitrobenzene-1,3,5-triamine, which is a famous insensitive high-energy material. Running this alkylation in the traditional stirred reactors has a high risk of spill and eruption incidents because of the evaporation of large amounts of volatile side-products. In this work, a wiped film evaporator/distillation coupled technology was used to run this reaction in a continuous and safe way. The design of the operation parameters was based on thorough understandings on reaction kinetics, residence time distribution, and heat transfer capacity of the wiped film evaporator. The results showed that while the jacket temperature and feed speed could significantly affect the alkylation, the effect of feed temperature and rotating speed on this reaction could be neglected. Under the optimal operating conditions, the conversion of TNPG and yield of 1,3,5-triethoxy-2,4,6-trinitrobenzene were 99.4 and 98.9%, respectively. Compared to the batchwise operation, alkylation of TNPG using the wiped film evaporator/distillation coupled technology is better in terms of safety, evaporation ability, productivity, and yield.