The low thermal conductivity paraffin (PW) phase change materials (PCMs) coating with the copper tungstate (CuWO4) as the shell material are fabricated. Compared with the most phase change microcapsules (NePCMs) with the single function of heat storage, the as-prepared multifunctional microcapsules possess high stability, UV absorption, and photoluminescent properties. A three-factor, four-level orthogonal experimental method was employed to determine the optimal stirring speed, emulsifier content, and core/shell ratio for the samples. The maximum phase transformation enthalpy (Delta Hm) reaches 132.09 J g-1 and the encapsulation rate (ER) is 72.96 % when the core to shell ratio, the percentage of sodium dodecylsulfonate (SDS) and the stirring rate is 1:1, 0.29 % and 800 rpm, respectively. The obtained NePCM exhibited a regular spherical shape and an intact core-shell structure, and the average size of the microcapsules is about 560 nm. These microcapsules can be used to modify coatings, which show the low thermal conductivity, photoluminescence, and UV characteristics. According to the fluorescence spectroscopy test, the fluorescence quenching phenomenon will occur when the excess microcapsules is added to the coating. The increased proportion of microcapsules results in a better thermal insulation effect, but a deteriorate thermal conductivity.