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Adapting controlled release technologies to the delivery of non-viral vectors has the potential to overcome barriers that limit gene therapy. Controlled release systems can enhance gene delivery and increase the extent and duration of transgene expression relative to more traditional delivery methods. Delivery vehicles for controlled release are fabricated from natural and synthetic polymers, which function either by releasing the vector into the local tissue environment or by maintaining the vector at the polymer surface. Vector release or binding is regulated by the effective affinity of the vector for the polymer, which depends upon the strength of molecular interactions. These interactions occur through non-specific binding based on vector and polymer composition or through the incorporation of complementary binding sites (e.g., biotin-avidin). This review examines the delivery of non-viral vectors from natural and synthetic polymers, and presents opportunities for continuing developments to increase their applicability.