A strong pyro-catalytic dye degradation with an ultrahigh degradation efficiency (>99%) in hydrothermally synthesized pyroelectric BiFeO3 nanoparticles was achieved under a room-temperature cold-hot alternating excitation (between 27 °C to 38 °C). The pyro-catalysis originated from a combination of the pyroelectric effect and the electrochemical oxidation-reduction reaction. The intermediate products (hydroxyl radicals and superoxide radicals) of pyro-electro-catalysis were observed. Pyro-catalysis provides a highly efficient and reusable dye wastewater decomposition technology through utilizing environmental day-night temperature variation.