The maintenance and incremental growth of the alveolar bone at the tooth extraction site, to achieve the required height and width for implant restoration, remains a major clinical challenge. Here, the concept of restoring the electrical microenvironment to improve the effects of alveolar ridge preservation (ARP) was investigated in a mini-pig preclinical model. The endogeneous electrical microenvironment of the dental alveolar socket was recapitulated by fabricating a biomimetic ferroelectric BaTiO3/poly(vinylidene fluoridetrifluoroethylene) (BTO/P(VDF-TrFE)) non-resorbable nanocomposite membrane polarized by corona poling. The polarized nanocomposite membrane exhibited excellent electrical stability. After implantation with bone grafts and covering with the charged membrane in tooth extraction sites for three months, both the vertical and horizontal dimension resorption of the alveolar ridge were significantly prevented, as assessed by cone beam computed tomography (CBCT) analyses. Micro-CT analysis showed that the charged membrane induced significant enhancement of newly regenerated bone at the tooth extraction sites. Histological analysis further confirmed that the restoration of the electrical microenvironment significantly promoted buccal alveolar bone regeneration and maturation. In addition, the charged membranes can maintain their structural integrity during the entire implantation period and exhibit positive long-term systemic safety, as assessed by preclinical sub-chronic systemic toxicity. These findings thus provide an innovative strategy for restoring the electrical microenvironment to enhance ARP following dentition defect and edentulism, which could further advance prosthodontics implant technology.