Biorefineries aim to convert biomass to a spectrum of products ranging from biofuels to specialty chemicals. To achieve economically sustainable conversion it is crucial to streamline the catalytic and downstream processing steps. Here we report a route that integrates bio- and chemical catalysis to convert glucose into bio-based unsaturated nylon 6,6. An engineered strain of Saccharomyces cerevisiae, with the highest reported muconic acid titer of 559.5 mg L-1 in yeast, was used as the initial biocatalyst to convert glucose into muconic acid. Without any separation, muconic acid was further electrocatalytically hydrogenated to 3-hexenedioic acid with 94% yield, despite the presence of all the biogenic impurities. Bio-based unsaturated nylon 6,6 (unsaturated polyamide 6,6) was finally obtained by polymerization of 3-hexenedioic acid with hexamethylenediamine, demonstrating the integrated design of bio-based polyamides from glucose.