The design and construction of magnetic semiconductor-based nanoreactor with high activity and selectivity toward highly toxic pollutant is a ground-breaking investigation for practical photocatalytic applications. Here, uniformly distributed ion imprinted ZnFe2O4 was compounded by employing ion imprinting technique with microwave-assisted. Extremely high toxic Cr(VI) (chromate and dichromate) was able to be selectively reduced to innoxious Cr(III) due to existence of quite a number of Cr(VI) imprinted cavities, Cr(VI) was directly reduced by e-in the imprinted layer (reduction rate reached 92.67%). Significantly, modification of mesoporous channels in the imprinted layer facilitated organic pollutants easily to contact with ZnFe2O4, which ensured the simultaneous photocatalytic degradation of tetracycline (C/C-0 = 0.416) in different reaction channels. With a promoted stability for recycling, our research offered a creative and practical technique for efficient identification and selective reduction of targeted ion among abundant ions, with simultaneous degradation of complex organic contaminants.