The invention belongs to the field of new chemical materials, and particularly relates to a praseodymium-doped cerium fluoride/attapulgite up-conversion composite photocatalytic material and a preparation method and application thereof. Pr(NO3)3.6H2O, Ce(NO3)3.6H2O, NH4F and attapulgite are added into deionized water for dissolution respectively, the system pH is adjusted to 4-5, and magnetic stirring is conducted to make the mixture evenly mixed; the mixture is transferred to a microwave hydrothermal reactor for reaction, the power is set to be 400 W, the reaction is carried out for 1-3 h, the temperature is set at 150-170 DEG C, a prepared sample is subjected to centrifugalization separation, then the sample is dried and ground, and thus the praseodymium-doped cerium fluoride/attapulgiteup-conversion composite photocatalytic material is prepared. The material can be applied to the field of photocatalytic desulfuration, and under sunlight for 3 h, the desulfulration rate can reach 95%.