This work reports on a very effective route to produce bio-based polyurethanes (PUs) and composites with high content of renewable carbon sources. The PUs are prepared with polyols synthesized from macauba oil (Acrocomia aculeata) and methylene diphenyl diisocyanate, at different [NCO]/[OH] molar ratios. Later, biocomposites are prepared with the as-obtained PUs reinforced with coconut husk fibers. The successful synthesis of natural oil-based polyols is ascribed to the hydroxylation and consumption of carbon-carbon double bonds in the fatty acid chains of the original starting oil as attested by FTIR spectroscopy. According to different thermal analysis techniques (TG, DTG, and DTA), the increase in the [NCO]/[OH] molar ratio improves the thermal stability of PUs, likely due to an increase of crosslinks. Dynamic mechanical analysis evidences the reinforcement effect of coconut husk fibers in bio-based PUs. The present PUs and composites are of low-cost and environmentally friendly materials for structural applications.