We report the remarkable effect of a small amount of poly(2-dimethyl amino ethyl methacrylate) ( PDMA) or PDMA-b-poly(N-isopropyl acrylamide) copolymer on the composition and the sol fraction of amphiphilic co-network (APCN) gels formed by the sequential nucleophilic substitution reaction between activated halide terminated polycaprolactone (PCL) and tertiary amine functional agarose or dextran. PDMA or its copolymer dramatically lowered the sol fraction, phase separation and enhanced the mechanical properties of the gels. APCN gels with pH- or both pH- and temperature-responsive behavior have been synthesized by the use of suitable amount of PDMA or its copolymer. Differential scanning calorimetric analysis, dynamic mechanical analysis, sol fraction and the composition of the gels revealed that PDMA or its copolymer showed enhanced miscibility with PCL and polysaccharides and acts as a reactive compatibilizer during the synthesis of the gels. These gels were degradable and exhibited good cytocompatibility and blood compatibility. These types of gels are suitable for sustained release of drugs and tissue engineering scaffold. (C) 2016 Elsevier Ltd. All rights reserved.