Based on the preparation of graphene oxide-ferroferric oxide composite (GO-Fe₃O₄) by chemical co-precipitation, hydrophobic modification of GO-Fe₃O₄ was carried out via physical adsorption using D2EHPA to obtain the D2EHPA@GO-Fe₃O₄ composite material (GOFP). Subsequently, a W/O-type GO-Fe₃O₄-based Pickering emulsion was successfully constructed using sulfonated kerosene as the oil phase, 1 mol/L hydrochloric acid as the internal aqueous phase, P507 (extractant) as the mobile carrier and GOFP as the solid emulsifier, which was used to extract heavy rare earth ion Ho³⁺. The effects of extraction time, mobile carrier dosage, emulsion-to-aqueous phase ratio, feed solution pH, and initial Ho³⁺ concentration on the extraction rate of Ho³⁺ were systematically investigated. The results indicate that under optimal conditions of extraction time of 3 min, feed solution pH ≥ 4.6, initial Ho³⁺ concentration of 0.002 mol/L, P507 (extractant) dosage of 0.5 mL, and emulsion-to-aqueous phase ratio of 0.3, the extraction rate of Ho³⁺ reaches 88%. The GO-Fe₃O₄-based Pickering emulsion liquid membrane method demonstrates promising application potential.