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The modification of biochar is essential for the development of multifunctional biochar materials with enhanced remediation effects on contaminated water. In this work, a biochar-based microcatalyst with sunlight sensitivity was synthesized by a creative modification method that involved the rapid fabrication of MnO₂ microspheres by high-energy electron beam (HEEB) irradiation, and loading them into corn straw-derived honeycomb-like KOH-modified biochar (MBC) to obtain a sunlight-sensitive microcatalyst (SSM). The honeycomb-like structure of MBC facilitated the improvement in MnO₂ dispersion and photocatalytic property through confinement effect. The effects of photocatalyst dosage, initial chlortetracycline (CTC) concentration, solution pH, temperature and coexisting ions on the photocatalytic performance of SSM were systemically investigated. The results indicated that SSM could efficiently degrade CTC in water and swine urine under sunlight, and exhibited high stability against coexistence of urea, Cl⁻ and SO₄²⁻. Moreover, SSM showed good reusability in regeneration studies. This work provides a novel method for degrading CTC with potential application prospect.