Semiconductor heterojunctions can significantly enhance photocatalytic degradation efficiency by facilitating rapid interfacial charge transfer. This article is based on the galvanic-cell driven principle; porous silicon (P-Si) was prepared by the carbon-catalytic etching method, and ZnO was loaded on its surface via electroless chemical deposition technology to form a P-Si/ZnO heterojunction, which was applied to the degradation of Rhodamine B (RhB). At a deposition temperature of 90 °C, a flawless 1D hexagonal prism structure of ZnO was formed, allowing the P-Si/ZnO heterojunction to completely degrade RhB within 2 hours with a degradation rate of 100%. Compared with a single P-Si material, the degradation performance is improved by 1.7 times. The formation of the built-in electric field and the rapid charge transfer at the heterojunction interface realized the complete degradation of RhB organic pollutants. After 20 cycles of use, the photocatalytic degradation rate remains above 70%, demonstrating excellent stability and recyclability.