Piezoelectric materials can convert mechanical energy into electrical energy, and further piezocatalysis can be designed based on the product between piezoelectric effect and electrochemical redox effect, which is hopeful for the actual dye decomposition. Tourmaline is a natural mineral with spontaneous polarization, which is an ideal piezocatalytic material and is rarely reported in dye decomposition. In this work, after 100 mg tourmaline powder is vibrated for 120 min, the piezocatalytic dye decomposition ratios of rhodamine B (RhB), methylene blue, and methyl orange are ∼95%, ∼46%, and ∼23%, respectively. The corresponding first‐order reaction kinetic values for these three dyes are 0.02681, 0.00639, and 0.00246 min−1, respectively. By adjusting the pH value of the initial RhB solution to 5, the decomposition ratio can reach ∼99% after only 60 min of vibration. In the process of dye decomposition, it is determined that the main active substances are hydroxyl radicals and superoxide radicals via electron spin–resonance spectra test. The spontaneous polarization performance of tourmaline can effectively adsorb dye molecules to promote the catalytic reaction. Natural tourmaline minerals are abundant, low cost, and environmentally friendly making them suitable for large‐scale piezocatalysis of mineral materials.