The invention discloses a catalyst for biphenyl preparation and a preparation method and application thereof, and belongs to the technical field of chemical catalysis. The catalyst comprises nanogoldAu and an imidazolyl porous ion frame PCIF loaded with nanogold. The method comprises the following steps: putting benzene, a catalyst, a solvent and an additive into a closed reaction kettle, uniformly mixing, introducing oxygen into the reaction kettle, keeping the pressure of the reaction system in the kettle within the range of 8-20 atm, keeping the temperature of the reaction kettle within the range of 100-180 DEG C, and carrying out an oxidative coupling reaction to obtain biphenyl. The catalyst that is Au@PCIF has the advantages of rich ion sites, high nano-gold dispersity, high catalytic efficiency, a simple preparation process, stability, difficulty in decomposition, easiness in separation from a liquid phase, high precious metal utilization rate and the like, has high selectivityand conversion rate in biphenyl preparation, and has high industrial application value.