In this work, new, novel materials of Al_2-xHf_xO₃ have been successfully obtained via a self-propagating synthesis method. Results from X-ray diffraction (XRD) confirm that all samples were pure. Quantitative analysis from Reitveld refinements have shown an accurate results of hafnium (Hf) inclusion in the Al₂O₃ hexagonal crystal lattice. Morphologies of pure Al₂O₃ and Al_2-xHf_xO₃ materials were studied by scanning electron microscope (SEM). The Hf content were confirmed via energy dispersive X-ray (EDX) and the values obtained were identical to the synthesized values. UV-visible spectroscopy showed that Al_2-xHf_xO₃ materials exhibited band gap narrowing with respect to pure Al₂O₃ material. Band values were also dependent on Hf content.