In this study, composites of unsaturated polyester resin (UPR), synthesized from recycled polyethylene terephthalate (PET), with 10 to 40% in volume of corn straw fiber (CSF), were elaborated and studied the effect of fiber content on their physical and mechanical properties. The content of cellulose (48.97%), hemicellulose (24.06%), and lignin (6.59%) were determined by chemical characterization of CSF. The characteristic bonds of the UPR were identified as a cross‐linking network between the styrene monomer (ST) and the unsaturated polyester (UP) through FTIR. Two decomposition stages were observed by TGA–DTG. The results of physical and mechanical properties showed that as the fiber content increased in the UPR, the water absorption increased (0.6% to 2.56%), on the other hand, the density (1218.23 to 1150.28 kg/m3), flexural strength (50.58 to 26.98 MPa), flexural modulus (2.66 to 2.29 GPa), tensile strength (8.62 to 3.65 MPa), tensile modulus (1.18 to 0.43 GPa), and hardness (81.67 to 65.67 Shore D), they decreased. SEM analysis showed some defects in the fiber distribution in the UPR, which affected the mechanical properties of the composites. This research contributes to the development of new material from use of two waste materials for the benefit of the environment.