Synthesis of silica microspheres has been investigated by means of urea-formaldehyde resin hybridization in the presence of surfactants. Well dispersal and spherical hybrid microspheres are obtained in the presence of surfactants. The hybrid product from the P123 (PEO20-PPO70-PEO20) condition breaks down into shell-like debris after calcined at 600 ℃, while that of CTAB (cetyltrimethylammonium bromide) deforms severely and shrinks to the one-ninth of its precursor, however, the silica product from SDBS (sodium dodecyl benzene sulfonate) condition retains good morphology. The surface area of silica products obtained in the present of P123 and CTAB increase by 20% and 13% respectively, however, that of product remains constant with its pore volume and diameter decreased by half in the case of SDBS. Quantitative analysis showed that hybridization of silica nano-particles has been inhibited in the presence of surfactants, the amount of silica from the SDBS condition almost doubles after its impregnation in TEOS (tetraethyl orthosilicate) solution and this optimized geometry guarantees the integrity and stability of the silica microspheres.