Dimethyl ether (DME), as an environmental-friendly alternative refrigerant, has received broadly attention. Phosphonium-based ionic liquids with good thermophysical properties are regarded as promising absorbents in absorption refrigeration systems. In this work, the measurement of solubility behavior to DME in trihexyltetradecylphosphonium chloride ([P6,6,6,14][Cl]) was carried out from 278.15 K to 348.15 K by means of isochoric saturation method. Non-random two liquid (NRTL) model and Krichevsky-Kasarnovsky (K-K) model were used to correlate the experimental data. The absolute average relative deviation between experimental liquid mole fraction and calculated values was 0.739% and 1.517% for NRTL model and K-K model respectively. Based on the solubility results, the performance of single-effect absorption refrigeration cycle used DME/[P6,6,6,14][Cl] pairs was analyzed, and further compared with other working pairs composed of [P6,6,6,14][Cl].