Polyelectrolyte complex (PEC) membranes, represented by substances such as chitin and chitosan, possess properties suitable for biocompatible materials in terms of substance permeability and hydrophilicity/phobicity. In this study, 15 types of polyanions and 6 types of polycations were combined to prepare PEC membranes. In addition, the combination ratio of each polymer was changed to alter the surface charge balance of the PEC membrane. Human periodontal ligament was cultured on the PEC membranes obtained by various combinations to study cell attachment and growth. It was found that the combination of polycations and polyanions, the properties associated with polymer function groups, and the surface charge were particularly important factors affecting cell adhesion and proliferation. Among 270 types of PEC membrane tested, 74 types had higher cell adhesion rates and 28 had higher adhesion rates than the control.