The work aims to enhance the deeply coarsening effect of electrolytic copper foil. The surface treatment of 35 μm electrolytic copper foils was conducted by electro-deposition method, and the influence of sodium tungstate-HEC-SPS composite additive on surface morphology and performance of electrolytic copper foil was systematically studied by AFM, SEM, XRD, peel strength test, surface roughness test and cyclic voltammetry. The sodium tungstate-HEC-SPS composite additive in the coarsening solution promoted the uniformity and compaction of coarsening coating layer, and improved the effect of deep plating. When the additive amounts of HEC, SPS and sodium tungstate were 5, 50, 60 mg/L respectively, the comprehensive deep plating effect was the best and the roughness Rz and peel strength reached 7.504 μm and 2.139 N/mm separately. The performance indicator was better than that in coarsening sample treatment. The composite additive reduced the reductive spike potential from ?0.644 V to ?0.674 V, which significantly enhanced the polarization of the electrode. The rate of electro-deposition decreased from 33 μm/h to 29.8 μm/h, which inhibited the deposition effectively. The surface morphology of the nodule on the peak of copper foil peak turned from spininess into smoothness, and was improved obviously. Meanwhile, the preferential orientation of the copper foil coarsening layer accelerated the orientation from (111) and (200) to (220). Adding the sodium tungstate-HEC-SPS composite additive into coarsening solution can significantly enhance the deep plating effect of electrolytic copper foil, improve the peel strength and surface roughness, and promote the preferred orientation (220).