The utility model discloses a photonic crystal fiber and a surface plasma photocatalytic reaction device with the same. A plurality of air holes are formed in a fiber core of the photonic crystal fiber; and surface plasma photocatalysts are filled in some air holes of the photonic crystal fiber by a selective filling method. The surface plasma photocatalytic reaction device based on the photonic crystal fiber comprises a solid laser, a neutral filter, a vacuum chamber and a photocatalytic product collecting device, which are connected with one another in turn. Compared with the prior art, the device takes the photonic crystal fiber as a carrier of a light transmitting medium and a catalyst, and meanwhile, as a reactant transfer channel, the device has the advantages of high energy density, high bean quality, high electro-optical conversion efficiency and easiness in optical fiber coupling with combination of laser, and can effectively enlarge and prolong the contact area and the reaction time of gaseous reactants and the catalyst and improve the utilization rate of laser energy.