Technical Abstract: Composite hydrogels of pectin and polyacrylamide were synthesized and evaluated by scanning electron microscopy, atomic force microscopy, light microscopy, and by dynamic mechanical analysis. The cross-linking polymerization of acrylamide in pectin solution resulted in a composite having a macroporous pectin domain with an interstitial polyacrylamide domain. This composite had improved mechanical properties compared to either polymer alone, and it absorbed and retained more water than cross-linked polyacrylamide alone. Furthermore, cross-linking polymerization of acrylamide in an existing pectinate scaffold resulted in a double network architecture, where filamentous polyacrylamide networks penetrated through pores of the pectin scaffold. It was found that pectins dictated the features of microstructure in the composites through regulating the coordination of phase separation of the two components and water partition between the two phases. Results from this study highlight potential new uses of pectins in protecting the physical structure of environmentally sensitive polymers from mechanical damage related to freezing, lyophilization, and other conditions experienced during their use in biomedical and industrial products.