The work aims to prepare a self-healing microcapsule of favorable thermotolerance and applicability to anticorrosive coating. Phenolic epoxy resin F-51 of favorable thermotolerance was modified by reactive diluent TMPEG. Urea-formaldehyde resin microcapsules were prepared through in-situ polymerization and nonionic surfactant composite emulsification. The distribution and the morphology of microcapsules were observed by optical microscope (OM) and scanning electronic microscopy (SEM). The particle size of the microcapsules was determined by laser particle sizer and its distribution was analyzed by combining with Gauss fitting. The effects of emulsifier selection, dosage, raw material ratio, agitation rate and other factors on the performance of the microcapsules were mainly discussed to study the most appropriate synthesis process. OM and SEM were used to observe shape of individual microcapsule and core-wall composition of the microcapsules was determined by combining with the principle of light diffraction. The functional group composition was characterized by fourier transform infrared (FT-IR) and the reaction activity of core material was determined by differential scanning calorimeter (DSC). The storage effects of microcapsules were tested in room temperature. The thermal weight loss of microcapsules was analyzed by thermogravimetric analysis (TGA). The self-healing microcapsules made of phenol-formaldehyde resin F-51 covered by polyurea formaldehyde were developed by using OP-10/JFC complex emulsifier. The results demonstrated that the production rate was up to 82% and particle was in centralized distribution with average particle size of 107 μm (dosage: 8% of core mass fraction, raw material ratio: 0.8:1 and agitation rate: 1600 r/min). Obvious light diffraction phenomenon was observed in OM. Corresponding characteristic absorption peak appeared in the characteristic curve of FT-IR. After the microcapsules were grinded with curing agent, corresponding curing reaction occurred. The rate of weight loss was less than 3.0% after being stored at room temperature for 100 days, and shell-core structure was kept complete within 250 ℃. Self-healing microcapsules of reactivity, favorable storage stability and thermal stability are successfully prepared, and the research results provide a reference for the development of self-healing anticorrosive coating.