The structural and optical properties of InAsxP1-x metamorphic buffers grown by metal–organic chemical vapor deposition on InP (100) substrates have been investigated. High-resolution X-ray reciprocal space mapping around the (115) InP lattice point reveals that the strain relaxations of the InAsxP1-x with x = 0.5, 0.55, and 0.7 are 98%, 92%, and 96%, while the lateral correlation lengths are 17, 62, and 28 nm, respectively. The optical bandgap energy of the InAsP derived from photoreflectance (PR) measurements decreases from 0.819 to 0.621 eV at 300 K when increasing As composition from x = 0.5 to 0.7. The bowing parameter for the optical bandgap of the InAsP is increased with increasing As composition, which is attributable to the increased spontaneous CuPt-type ordering in InAsP. It is found from the excitation power-dependent PR measurement that the InAsxP1-x layers have different degrees of the bandgap redshift due to the reduced thermal conductivity caused by crystal imperfections generated during the strain relaxation process.