Hyper-cross-linked polynaphthalene nanoparticles (PNNs) capable of catalyzing the degradation of organic pollutants upon exposure to visible light have been developed. The nascent and metal-free PNNs with a porous structure, high specific surface area, and narrow bandgap are chemically and thermally stable in the catalytic system, which make it promising as a kind of excellent photocatalytic material compared to conventional photocatalysts. The photo catalytic activity of the as-obtained PNNs exhibits remarkable photocatalytic perforniance for the degradation of rhodamine B (RhB) and methyl blue (MB) under the irradiation of visible light. The easy preparation,, high catalytic activity, and recyclability of the PNNs open new opportunities in the visible-light promoted degradation of organic pollutants.