With the constant upgrading of healthcare concepts, silicone-free hair products have attracted more attention among consumers. In the present study, transparent silicone-free shampoo containing proteins was successfully fabricated by mixing mild non-sulphate surfactants, compound cationic conditioners, natural silicone oil substitutes, protein conditioners, thickeners, and other auxiliary ingredients. The effects of the type of surfactants, hair conditioners and thickeners, the type and content of proteins, and the mass ratio of compound proteins on the hair foaming performance, hair grooming performance, and penetration performance were investigated. The basic formulation framework for transparent silicone-free shampoo was established at first. Then, various hydrolyzed proteins were further added to the basic formulation in the form of single use or compound use to prepare transparent silicone-free shampoo containing different proteins. The morphology of hair samples and penetration of protein in hair were evaluated with a scanning electron microscope and laser confocal fluorescence microscopy, respectively. And the hair grooming performance was also determined by a dynamic combing tester. The compound proteins of Croquat WKP PE-LQ-WD and Gluadin® Kera-PLM with mass ratios of 1:9 and 1:1 at 2 wt% total protein content added to the silicone-free shampoo brought a higher contact angle and a lower frictional coefficient than commercial silicone-free shampoo without proteins. In addition, the compound proteins also have the dual effect of adsorbing the hair surface and penetrating deep into the interior of the hair. The combination of cationic modified hydrolyzed protein (e.g., Croquat WKP PE-LQ-WD) and hydrolyzed protein with low molecular weight (e.g., Gluadin® Kera-P LM) at an appropriate mass ratio exhibited a strong synergistic effect on hair conditioning properties. It could provide a significant reference for developing silicone-free hair products with more benefits.