The hydrophobic surface properties of catalysts, generally overlooked in the field of sulfate radical-based advanced oxidation processes (SR-AOPs), have significant potential in anti-interference, self-cleaning, and anti-fouling in realistic wastewater treatment. The conflicting nature of hydrophobicity and catalytic activity presents considerable challenges in developing heterogeneous oxidation. To overcome such limitation, herein, different surfactants were employed to regulate the surface properties of CoCu-layered double hydroxides (LDH) for the activation of peroxymonosulfate (PMS). Our results demonstrated that by comparison with sodium dodecyl sulfate (SDS) and sodium laurate (SLA), sodium dodecyl sulfonate (SDSO) regulated LDH (SDSO-LDH) exhibited the most effective interpolation of organic anions into the interlayer space, simultaneously showing efficient ability for PMS activation and degradation of various emerging contaminants (ECs). The SDSO-LDH/PMS system also exhibited excellent stability and recyclability, with Co(IV)=O and SO4•- species working as the dominant oxidative intermediates. Density functional theory (DFT) calculations further confirmed the thermodynamic feasibility of these reactions. Moreover, the effective degradation of intrinsic organic substances in realistic wastewater and sustained hydrophobicity establishes SDSO-LDH a competitive candidate catalyst for SR-AOPs. The synergy between catalytic activity and hydrophobicity offers a novel perspective for the application of SR-AOPs in wastewater treatment.