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In this work, a photoelectrochemical reactor with an anode based on hybrid structure between conducting polymer polypyrrole (PPy) and porous silicon (PSi) was fabricated and utilized to evaluate the photocatalysis and electro‐assisted photocatalysis for degradation of rhodamine B (RhB) solution. The PSi was made of n‐type silicon single‐crystal wafer by the metal‐assisted chemical etching (MACE). The anode PPy/PSi formed following a polymerization of the PPy on the PSi from the vapour‐phase route using oxidant FeCl3. Typical material characterizations of the PPy, PSi and PPy/PSi were investigated via scanning electron microscope (SEM), and spectroscopies of Fourier‐transform infrared (FTIR), Raman scattering and UV‐vis. Under visible light radiation (halogen light with the wavelength region of 400–700 nm), photocatalytic and electro‐assisted photocatalytic processes of the reactor were conducted by degradation of the RhB solution. A heterojunction (p‐n) of the PPy/PSi was proposed to explain the efficient catalytic performance of the reactor. [ABSTRACT FROM AUTHOR]