Polymer membranes have been widely used in guided tissue regeneration (GTR) and guided bone regeneration (GBR). The literature recognizes that poly (lactic acid) (PLA)/poly (ε-caprolactone) (PCL) blends have better physicochemical properties and that a porous polymer surface facilitates cell adhesion and proliferation. In addition, hydroxyapatite (HAp) incorporated into the polymer matrix promotes osteoinduction properties and osteoconduction to the polymer-ceramic biocomposite. Therefore, polymer membranes of PLA/PCL blend with the addition of HAp could be an alternative to be used in GBR. HAp was obtained by precipitation using the mixture of solutions of tetrahydrate calcium nitrate and monobasic ammonium phosphate salts. The porous membranes of the PLA/PCL (80/20) blend with the addition of HAp were obtained by solvent casting with a controlled humidity method, with the dispersion of HAp in chloroform and subsequent solubilization with the components of the blend. The solution was poured into molds for solvent evaporation under a controlled humidity atmosphere. The membranes showed the formation of pores on their surface, together with dispersed HAp particles. The results showed an increase in the surface porosity and improved bioactivity properties with the addition of HAp. Moreover, in biological studies with cell culture, it was possible to observe that the membranes with HAp have no cytotoxic effect on MC3T3 cells. These results indicate a promising use of the new biomaterial for GBR.