Composites of hydrated calcium phosphate cement (CPC) and bioactive glass (BG) containing Si were immersed in vitro to study the effect of chemical composition on surface reaction layer formation and dissolution/precipitation behavior. The solutions used were 0.05M tris hydroxymethyl aminomethane/HCl (tris buffer), tris buffer supplemented with plasma electrolyte (TE) with pH 7.4 at 37°C, and this solution complemented with 10% newborn bovine serum (TES). The post-immersion solutions were analyzed for changes in Ca, PO4 and Si concentrations. The reacted surfaces were analyzed using Fourier transform infrared (FTIR), and scanning electron microscopy (SEM) with energy dispersive X-ray analysis (EDX). The sample weight variations after immersion were also determined. The results showed that the composition of the bioactive composite CPCs greatly affected their behavior in solution and the formation of apatite bioactive surface reaction layers. After immersion in TE solution, Ca ions were taken up by all samples during the entire immersion duration. Initially, the P ion concentration increased sharply, and then decreased. This reaction pattern reveals the formation of an amorphous calcium phosphate layer on the surface of these composite calcium phosphate cements. FTIR revealed that the layer was, in fact, poorly crystallized Ca-deficient carbonate apatite. The thickness of the layer was 12-14 μm and was composed of rod-like apatite with directional arrangement. For immersion in TES solution, the Ca and Si ion concentrations showed a similar behavior as that in TE, but the release rate of Si ion was higher. FTIR revealed that after TES immersion, not only did the typical, poorly crystallized, Ca-deficient carbonated apatite form, as it did in TE, but that the serum proteins co-adsorbed on the surface and thereby affected the surface reaction layer formation. A thinner apatite layer was formed and was composed of a micro-porous layer comprising rounded particles in a glue-like appearing matrix. The addition of BG to the calcium phosphate cements to create composite calcium phosphate cements obviously is at the basis of this altered behavior of the cements. All data combined are useful for the design and optimization of degradable implant materials for use in bone tissue repair and regeneration procedures.