Background: This study investigated the use of in situ polyelectrolyte complex formation by using two oppositely charged polysaccharides [Chitosan (cationic), Sodium Alginate (anionic)]. It forms 3-D intercalation and interpenetrating network helping in controlling the release of highly acid-soluble Captopril. Objective: To develop a polyelectrolyte complex based single unit gastroretentive tablet by using optimization based 3 (2) Taguchi factorial design for controlled delivery of Captopril. Materials and Methods: Gastroretentive Captopril tablets were prepared by the direct compression technique. Total 09 batches were prepared as per 3 (2) Taguchi factorial design studies of 100 tablets each. Results: Thermal analysis method revealed that there is a formation of PEC between chitosan and sodium alginate. In vitro buoyancy and T60%, drug release studies revealed that due to complex formation, formulation remains stable and remains buoyant. From factorial design studies, it was interpreted that for buoyancy time (Y1) chitosan desired effect value was found higher. For 60% drug release (T60%; Y2) both chitosan and sodium alginate have a synergistic effect. Durbin Watson's statistical model and residual data suggested that the model is statistically validated. All formulations follow the zero-order kinetics. Stability studies revealed that formulations F5 and F9 remain stable for long-term stability studies without showing any significant changes. The fit analysis studies indicated that the prepared formulation was different from the innovator product indicating low f1 and f2 values. Conclusion: From the result generated it was concluded that chitosan-sodium alginate polyelectrolyte complex has sufficient potential to retard the release of CPT.