The work aims to improve performance of melamine-formaldehyde resin microencapsulated red phosphorus (MRP), modify it in sol-gel method, and study the optimum technological conditions. With tetraethoxysilane (TEOS) as precursor and TEOS additive amount as process conditions, silica gel-MF resin double layered microencapsulated red phosphorus (Si-MRP) was prepared via sol-gel modification. Surface morphology and coating effect of Si-MRP were characterized by FT-IR, SEM and XPS. Meanwhile, moisture rate, thermal stability and sensitivity of the samples were also tested. A layer of silica gel structure was introduced on the surface of MRP in sol-gel method successfully to coatsilica gel-MF resin double layered microencapsulated red phosphorus (Si-MRP). The morphology and coating ratio of Si-MRP was influenced by the TEOS additive amount. With the increase of TEOS, surface morphology of Si-MRP transformed from stratiform structure to particle accumulation structure, and the coating ratio decreased from 97.5% to 93.6%. The silica gel structure enhanced thermal and mechanical stability of MRP, and decreased moisture rate. Provided with TEOS-MRP mass ratio of 1:2.5, ignition temperature of Si-MRP prepared increased by 80 ℃ compared with MRP, and the moisture rate and friction sensitivity decreased to 3.7% and 14%, respectively. MRP can be microencapsulated effectively in sol-gel method, and performance of the samples can be further improved after microencapsulation.