A new class of highly active solid base catalysts for biodiesel production was developed by creating hierarchically porous aluminosilicate geopolymer with affordable precursors and modifying the material with varying amounts of calcium. For the catalysts containing ≥8 wt% Ca, almost 100% conversion has been achieved in one hour under refluxing conditions with methanol solvent, and the high catalytic activity was preserved for multiple regeneration cycles. Temperature-programed desorption studies of CO2 indicate that the new base catalyst has three different types of base sites on its surface whose strengths are intermediate between MgO and CaO. The detailed powder X-ray diffraction (PXRD) and X-ray photoelectron spectroscopic (XPS) studies show that the calcium ions were incorporated into the aluminosilicate network of the geopolymer structure, resulting in a very strong ionicity of the calcium and thus the strong basicity of the catalysts. Little presence of CaCO3 in the catalysts was indicated from the thermogravimetric analysis (TGA), XPS and Fourier transform infrared spectroscopy (FT-IR) studies, which may contribute to the observed high catalytic activity and regenerability. The results indicate that new geopolymer-based catalysts can be developed for cost-effective biodiesel production.