The work aims to prepare binary composite core microencapsulated phase change material and investigate the effects of different ratio dodecanol/decanol on the properties and morphologies of the microcapsules. The binary composite core microencapsulated phase change material was prepared by in-situ polymerization with binary combination phase change material dodecanol/decanol as the core materials and urea and methyl aldehyde as the raw material for the wall. The properties of the products were analyzed and characterized by SEM, TGA and DSC. Experimental results showed that the phase change temperature of the microcapsules went up with the increased proportion of dodecanol, while the latent heat and decomposition temperature did not change significantly. Microcapsule particle size was distributed relatively uniformly, but the surface of the microcapsules was getting more and more rough with tiny particles and the aggregation phenomenon was more and more obvious with the increased proportion of dodecanol. In conclusion, when the proportion of dodecanol and decanol keeps 1︰1, the appearance of the microcapsule is nearly spherical, the surface is dense and smooth, and it disperses best.