Due to its excellent conductivity, good thermal stability and large specific surface area, carbon nano-tubes (CNTs) were selected as support to prepare a Re-based catalyst for dimethyl ether (DME) direct oxidation to polyoxymethylene dimethyl ethers (DMM x ). The catalyst performance was tested in a continuous flow type fixed-bed reactor. H 3 PW 12 O 40 (PW 12 ) was used to modify Re/CNTs to improve its activity and selectivity. The effects of PW 12 content, reaction temperature, gas hourly space velocity (GHSV) and reaction time on DME oxidation to DMM x were investigated. The results showed that modification of CNT-supported Re with 30% PW 12 significantly increased the selectivity of DMM and DMM 2 up to 59.0% from 6.6% with a DME conversion of 8.9%; besides that, there was no CO x production observed in the reaction under the optimum conditions of 513 K and 1800 h´1. The techniques of XRD, BET, NH 3 -TPD, H 2 -TPR, XPS, TEM and SEM were used to characterize the structure, surface properties and morphology of the catalysts. The optimum amount of weak acid sites and redox sites promotes the synthesis of DMM and DMM 2 from DME direct oxidation.