This study identifies the role and significance of heat treatment parameters on blood compatibility and hemostatic performances. Bioactive nanomaterials step annealed at 550 and 600°C enhances the biocompatibility due to the liberation of nitrate content. This also develops the anisotropic structures such as needle‐like and rod‐like appearances that positively improve the erythrocyte compatibility. Different stable crystalline phases such as NaCaPO4, Na2Ca2Si3O9, and Na1.8Ca1.1Si6O14 were observed for all the bioactive materials, whereas in the case of 800°C, phase transition of Na3CaPSiO7 was perceived along with P2O5. Alternatively, morphology varied from cubical (600°C) to rod‐like (step annealing) and further turned toward flake‐like (800°C) structures. Step‐annealing process decomposed the nitrate groups as well as maintained the glass network without altering the crystalline phases. As a result, bioactive nanomaterials subjected to step annealing at 550°C along with 600°C exhibited superior compatibility with erythrocytes. Bioglass heat treated at 800°C revealed incredible blood clotting efficacy, in which Ca2+ ions initiated the thrombotic effect, blood components were concentrated due to the effect of calcium, and enhances the hemostatic performance. Bioactive glass annealed below 800°C facilitates the biocompatibility, subsequently encourage bone ingrowths at in vivo. Bioglass‐800°C inspired the fibrin formation and induced clot as a hemostat to control hemorrhage.