Because of the current interest in sustainability, environmental stewardship, and green chemistry, there has been a lot of interest in using agro-based raw materials for the design of polymeric materials. One of the promising biorenewable materials is sucrose, which is inexpensive and widely available. In this work we have carried out the synthesis of sucrose-toluene diisocyanate-based polyurethane through microwave-assisted reactions. Comparisons of conventional heat versus microwave reactions have been made. Microwave-assisted synthesis has been found to significantly decrease the reaction time and save energy relative to conventional heat. The sucrose polyurethane has turned out to be a suitable matrix to prepare semi-interpenetrating polymer networks (semi-IPNs) involving a second material. Two examples shown in this work are the semi-IPNs of sucrose polyurethane with polycaprolactone and soybean oil. Characterization of the polymers has been conducted with C-13 NMR, FT-IR, size exclusion chromatography, and thermal analysis.