Hydroxyapatite/bioactive glass laminate has been fabricated by hot pressing of stacked hydroxyapatite and bioactive glass powders at 1000°C (30min, 30MPa). This processing resulted in the formation of β-NaCaPO4 (β-rhenanite) interphase layers between each hydroxyapatite and bioactive glass layer. The β-NaCaPO4 interphase provided an easy path for debonding and crack deflection in the laminate demonstrating that this material can work as weak interphase in hydroxyapatite ceramics. The β-NaCaPO4 exhibits also high biocompatibility and bioactivity. Moreover, it significantly enhances sinterability of hydroxyapatite at 1000°C without formation of any undesired phases, such as tricalcium phosphate or CaO. Our results show that various microstructurally controlled hydroxyapatite-based composites with potentially improved reliability and high biocompatibility can be prepared in the hydroxyapatite/β-NaCaPO4 or hydroxyapatite/bioactive glass systems.