HPW@HKUST-1 from phosphotungstic acid (HPW) supported in HKUST-1 was prepared with one-pot synthesis. It had excellent catalytic performance in the etherification of isobutene and ethylene glycol to ethylene glycol monotert butyl ether (EGME). The structure of catalysts was analyzed by XRD, SEM, EDX, BET and ICP, and the acidity of catalysts was determined by pyridine infrared (Py-IR) and acid-base titration. The results showed that enhanced HPW loading amount increases the Br?nsted acid site of the catalyst, which was beneficial to improve the reactant conversion. Meanwhile, there was a negative correlation between HPW loading amount and the pore size of the catalyst, and the decrease of pore size was conducive to improve the EGME selectivity. The HPW@HKUST-1 catalyst loaded with 10% phosphotungstic acid (Molar fraction based on the amount of substance in HKUST-1) has better activity and good recyclability. The optimum reaction conditions were investigated and determined as follows: reaction temperature was 100 ℃, the molar ratio of isobutene to ethylene glycol (n(IB):n(EG) )was 6:1, and catalyst dosage was 10% of the mass of ethylene glycol. The ethylene glycol conversion in optimal conditions reached 97% and EGME selectivity was 85% respectively.