The coupling of photocatalysis and piezocatalysis has gained significant interest among researchers. In this study, we present the photo-piezocatalytic activity exhibited by bismuth titanate (Bi4Ti3O12) glass-ceramics (BTO-GC). BTO-GC samples were prepared in a glass system of 40Bi2O3-40B2O3-20TiO2 (in mol %) by using the melt-quench technique. The catalyst was characterized by the X-ray diffraction (XRD) technique and Raman spectroscopy for its structure and phase analysis. Surface morphology and chemical composition were analyzed by scanning electron microscopy (SEM) and X-ray photoelectron spectroscopy (XPS), respectively. The catalytic performance of BTO-GC was evaluated in photocatalysis, piezocatalysis, and photo-piezocatalysis processes. Methylene blue (MB) dye degradation was evaluated by using a UV–Vis spectrophotometer. A maximum degradation performance of ~86% was achieved in the solar light photocatalysis process. This study highlights the synergistic photo-piezocatalytic performance in glass-ceramics and advances the understanding of its underlying mechanism.