Display omitted •A hollow, hydrophilicity surface molecularly imprinted materials were prepared.•Materials possess photocatalytic, reusability, and highly selectivity.•The removal contains of targeted adsorption, photocatalytic degradation.•Materials exhibited favorable adsorption capacity and selectivity towards SDZ.•The photodegradation of SDZ maintains 90.00 % after 6 cycles. Novel hollow C, N-TiO2@C surface molecularly imprinted microspheres (HCNTC-SMIPs) with hydrophilicity, reusability, and selectivity were synthesized. The core–shell hollow structure yields large specific surface areas, high surface-to-volume ratios and effective diffusion rate on both inner and outer exposed surfaces. The C, N-TiO2 shell possesses high photo-catalytic decomposition capacity toward the specific pollutants. Moreover, TiO2 acts not only as a photocatalyst but also as a double cross-linker agent of molecularly imprinted to significantly reduce the molar ratio of formaldehyde. The hydrophilic surface imprinted layer provides the recognition sites and specific pore structures. The results showed that HCNTC-SMIPs possessed a high specific surface area of 305.10 m2 g−1 and a good visible light harvesting property with a bandgap of 1.67 eV. This could efficiently suppress the photoelectron-hole recombination, and thereby heightening the photocatalytic degradation of sulfadiazine (SDZ). The photodegradation efficiency of HCNTC-SMIPs can reach 99.25 % within 140 min and 90.00 % after 6 cycles. The HCNTC-SMIPs had a higher kinetic constant (0.01815 min−1) than those of HCNTC (0.00964 min−1) and TiO2 (0.00548 min−1). HCNTC-SMIPs can achieve targeted and efficient SDZ removal, as well as in-situ regeneration. The possible degradation pathways of SDZ primarily includes smiles-type rearrangement, SO2 extrusion, ring hydroxylation, direct oxidation and SN bond cleavage processes based on LC-MS analysis.