The mechanism for tourmaline powder improving the photocatalysis effect of nano-TiO2 was studied by electron-spin resonance (ESR). It is found that the intensity of the signal of hydroxyl free radical produced by the mixture of the tourmaline and nano-TiO2 through 355nm wavelength ultraviolet radiating is increased. Under natural light, the mixture of nano TiO2 and tourmaline powder in a certain weight ratio can improve the effect of decomposing methyl orange that proved that the ESR result was right. The tourmaline particle could promote the photocatalysis of nano-TiO2. This result may be due to the surface electric field of the tourmaline, which can absorb the particle of nano-TiO2 and make the electron inspired by photon transfer from the inner of nano-TiO2 particle to its surface, and even make the electron transfer into tourmaline particle.