This is a comprehensive study reporting the fabrication of highly porous Gehlenite scaffold (Ca2Al2SiO7)—both with and without surface modification—for the first time. The sintering temperature of Gehlenite scaffolds was optimized. Next, the optimized Gehlenite scaffold was coated by polycaprolactone (PCL)-Forsterite (Mg2SiO4) nanocomposite to improve the scaffold’s brittleness and biological properties. 1375 °C was found to be the optimized sintering temperature by which the Gehlenite scaffold was consolidated. Different PCL and Forsterite concentrations were separately applied on the optimized scaffold to yield a complete nanocomposite coating without clogging the macroporous structure. The bioactivity, degradation rate, cell viability, attachment and proliferation of three different scaffolds—non-coated (sintered at 1375 °C), PCL-coated and PCL/Forsterite nanocomposite-coated—were scrutinized and compared to each other in vitro. Based on our results, it is concluded that the PCL-Forsterite nanocomposite-coated scaffold with desired physical, chemical and biological-related properties has a great potential for bone tissue regeneration.