This study aims to develop a methodology for analysis of physicochemical characteristics of municipal solid waste incineration (MSWI) fly ash. In this work, microstructure, particulate size distribution and components of fly ash were investigated using SEM, laser particulate description analyzer, ICP, XRF, IR and XRD. It is found that content of chemical components follows sequence of CaO ≫ SiO2 ≫ Al2O3 ≫ Fe2O3 ≫ MgO ≫ K2O ≫ Na2O, and fly ash registers a SiO2–Al2O3–metal oxides system as total content of these oxides exceeds 80%. Major mineralogical components of fly ash involve SiO2, CaCl2, Ca3Si2O7, Ca2SiO4•0.35H2O, Ca9Si6O21•H2O, K2Al2Si2O8•3.8H2O and AlCl3•4Al(OH)3•4H2O. Glass phases account for around 57%, which is conducive to reduction of energy consumption in recycling of the ash.