Ti/bioglass composite coatings on titanium alloy were prepared by a subsonic thermal spraying technology. Mixtures of titanium and bioglass powders with different proportions were used as feedstock. The effect of soaking of bioglass on the bond strength of between coatings and substrate was discussed. The bond strength and residual stress were investigated. The morphology was observed using scanning electron microscopy (SEM). The results showed that TiO2, CaTi4(PO4)6, CaTiO3, NaTi2(PO4)3 formed during thermal spraying process and the residual stress in the coatings was in compressive state. After the coatings were heat-treated, soaking of bioglass made some particles achieve metallurgical bond. Furthermore, new bioglass was formed and the compressive stress was increased. The phenomenon of bioglass healing up the cracks in the heat-treated coatings was observed through SEM, which reduced the porosity of the interface layer resulting in the significant increase of the bond strength.