This study evaluated bond strengths of three commercial veneering porcelains to experimental cast titanium-chromium (Ti-Cr) alloy and commercially pure titanium (cp-Ti) via three-point bending test. After the bending test, the fractured specimens were analyzed using an electron probe microanalyzer (EPMA). The Ti-Cr specimens showed lower bond strengths than the cp-Ti specimens, irrespective of the layering porcelain material; however, all the strengths exceeded the minimum requirement of ISO 9693-1:2012 (>25 MPa). EPMA revealed that titanium and/or chromium elements were detected on the debonded porcelain surface of the Ti-Cr and cp-Ti specimens in the case of the higher bond strength. Contrastingly, the residual porcelain was retained on the metallic surface in the case of the lower bond strength. Although porcelain bonding to the titanium alloy is influenced by porcelain type, the Ti-Cr alloy could be feasible for porcelain-fused-to-metal restorations.