The work aims to study the effect of different HLB values (hydrophilic lipophilic balance of surfactant) of compound emulsifiers Span-80/Tween-80 and SDBS/Triton X-100 on agglomeration phenomenon of n-tetradecane/mel- amine-formaldehyde shell microcapsules. The HLB value of two series of compound emulsifiers were adjusted. N-tetradecane/melamine-formaldehyde shell microcapsules were prepared through in-situ polymerization. The chemical structure, morphology and thermal properties of the prepared phase change microcapsules were observed by fourier transform infrared spectroscopy (FTIR), scanning electronic microscope (SEM), differential scanning calorimeter (DSC) and thermogravimetry analysis (TGA). Phase change microcapsules prepared with compound emulsifier Span-80/Tween-80 had good morphologies and thermal properties, and less agglomeration phenomenon when the HLB of compound emulsifier Span-80/Tween-80 was 12.03. Microcapsules prepared with compound emulsifier SDBS/Triton X-100 had good morphologies, particle size distribution & dispersity, thermal stability and less agglomeration phenomenon when the HLB was 12.78. A higher latent heat of 135.6 J/g was obtained. Emulsifier’s HLB has significant influences on melamine-formaldehyde phase change microcapsules.