BACKGROUND Potato protein possesses strong potential for application in the food industry due to its outstanding nutritional and functional properties. However, the inevitable industrial processing often brings adverse effects. The use of a polysaccharide and protein complex is a promising way to improve the performance of potato protein. This work aimed to investigate the effects of different physical factors on the potato protein/chitosan (PP/CS) complex system. RESULTS The addition of NaCl was not conductive to the formation of PP/CS complexes, resulting in significantly decreased peak turbidities from 1.29 to 0.75. The effect of different ions on PP/CS system matched with the Hofmeister series in the following order: Li+ > Control > Na+ > K+; SCN− > I− > NO3− > Br− ≈ Control > Cl− > SO42−, among which the salting‐in ions (Li+, Br−, NO3−, I− and SCN−) tended to promote the formation of PP/CS complexes. The turbidity increased significantly when the reaction temperature rose to 45 °C and above, and peak turbidity was obtained at lower pH values. The PP/CS system reaction at 45 °C led to the highest whiteness value, and the Maillard reaction could occur when the temperature was above 45 °C. CONCLUSIONS The results of the present study confirmed that different physical factors led to strong influences on PP/CS complexes, especially when considering the Hofmeister series and the Maillard reaction. These findings could have significant implications for the utilization of potato protein in complex food systems. © 2023 Society of Chemical Industry.