Organic perlite (organo-perlite) hybrids were synthesized by ion-exchange interaction of natural perlite with dioctadecyl dimethyl ammonium bromide (DDAB) at different cation exchange capacity (CEC) equivalents of perlite. The morphology and structure of perlite and organo-perlite hybrid products were characterized by WCA, zeta-potential analyzer, SEM, surface area analyzer, FT-IR, QCM-D, AFM, and interfacial rheometer. The surface wettability of perlite was changed from highly hydrophilic to hydrophobic after modification with loaded cationic surfactants, and the inversion of negative to positive charge occurred. It was also found that physical modification of perlite with the cationic surfactant DDAB equivalent to 2.0 CEC of perlite resulted in the preparation of organo-perlite hybrids with better hydrophobicity. Therefore, organo-perlite hybrids at 2.0 CEC equivalent surfactant loading were used to remove emulsified oil from simulated alkali/surfactant/polymer produced water. The experimental results demonstrated that the initial pH, dosage, temperature, and contact time had significant effects on the treatment of oily wastewater. The oil removal efficiency was 99.75% at 60 °C and pH 6. The results indicate that organo-perlite hybrids are highly promising adsorbent materials with broad applications in the fields of oily wastewater treatment and environmental protection.