The growth and optical properties of InP and InP/InAs nanostructures on GaAs nanowires are investigated. InP quantum well and quantum dots (QDs) are formed on the sidewalls of GaAs nanowires successively with increasing the deposition time of InP. The GaAs/InP nanowire heterostructure exhibits a type-II band alignment. The wavelength of the InP quantum well is in the range of 857–892 nm at 77 K, which means that the quantum well is nearly fully strained. The InP quantum dot, which has a bow-shaped cross section, exhibits dislocation-free pure zinc blende structure. Stranski-Krastanow InAs quantum dots are subsequently formed on the GaAs/InP nanowire core-shell structure. The InAs quantum dots are distributed over the middle part of the nanowire, indicating that the In atoms contributing to the quantum dots mainly come from the vapor rather than the substrate. The longest emission wavelength obtained from the InAs QDs is 1039 nm at 77 K. The linewidth is as narrow as 46.3 meV, which is much narrower than those on planar InP substrates and wurtzite InP nanowires, suggesting high-crystal-quality, phase-purity, and size-uniformity of quantum dots.