In situ synthesis technique of β-tricalcium phosphate(β-TCP)/ Na-doped 58S bioglass composite powders were investigated. Firstly, the β-TCP ultra-micro powders are synthesized via wet chemical method. β-TCP/Na doped 58S bioglass composite powders were synthesized in situ by sol-gel technique, using tetraethyl orthosilicate(TEOS), triethyl phosphate(TEP), calcium nitrate tetrahydrate(Ca(NO3)2•4H2O), sodium nitrate(NaNO3) as starting materials. The composite powders were characterized by XRD, EDX and SEM. The bioactivity of the synthesized powders was analyzed by immersion studies in simulated body fluid (SBF). The results show that the composite powders are made up of good crystalline β-TCP and amorphous bioglass, and it was conformed that the material had good osteoproduction and bioactivities, that is an indication of bioactive potential in vivo. It is believed that the β-TCP/ Na-doped 58S bioglass (58SN) composite by sol-gel technique in situ could be a desirable biomaterial for preparing scaffold of bone tissue engineering.