A kind of solid-solid phase change materials (SSPCMs), melamine/formaldehyde/polyethylene glycols (MFPEG) crosslinking copolymers, was synthesized referring to the reaction mechanism and conditions of amine-aldehyde condensation reaction and aldolization. The composition and chemical structure, thermophysical and crystallographic properties of MFPEG crosslinking copolymers were investigated by Fourier transform infrared spectroscopy (FT-IR), H-1 nuclear magnetic resonance spectrometer (H-1 NMR), differential scanning calorimetry (DSC), thermogravimetry analysis system (TGA), wide-angle X-ray diffraction (WXRD) and polarization optical microscopy (POM). The results indicate that MFPEGs crosslinking copolymers possess excellent phase change properties and an applicable temperature range. The maximal latent heat enthalpies of heating and cooling cycle are 109.4 and 103.9 J/g, respectively. The decomposing temperature range of MFPEGs is about 340-455 degrees C in nitrogen atmosphere. (C) 2014 The Authors. Published by Elsevier B.V. This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/3.0/).