ObjectiveWith 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 of mild non‐sulfate surfactants, compound cationic conditioners, natural silicone oil substitutes, protein conditioners, thickeners and other auxiliary ingredients. Effects of the type of surfactants, hair conditioners and thickeners, the type and content of proteins, and mass ratio of compound proteins on the hair foaming performance, hair grooming performance and penetration performance were investigated.MethodsThe basic formulation framework of 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 was evaluated with a scanning electron microscope and a laser confocal fluorescence microscopy, respectively. And the hair grooming performance was also determined by a dynamic combing tester.ResultsThe compound proteins of Croquat WKP PE‐LQ‐WD and Gluadin® Kera‐PLM with the mass ratio of 1:9 and 1:1 at 2 wt% total content of proteins added into the silicone‐free shampoo brought higher contact angle and 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.ConclusionThe 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 appropriate mass ratio exhibited a strong synergistic effect of hair conditioning properties. It could provide a significant reference for developing silicone‐free hair products with more benefits.