Photoreflectance is a contactless type of modulation optical spectroscopy. It is used to study the band structure features of monocrystalline semiconductors, their doping level, the composition of alloys, as well as surface and interface band bending. Using high-quality GaAs as an example, the possibilities of describing the photoreflectance lineshape by one-electron and exciton models are demonstrated. The spectra of ultrapure samples of this material exhibit an oscillating structure well described by excitonic effects. For III-V alloys, a review of photoreflectance results concerning the effect of composition and temperature on the band gap and spin-orbit splitting is carried out. Determination of the position of the Fermi level on the surface (Fermi level pinning) for III-V crystals is considered. The currently developing technique for measuring photoreflectance in the mid-infrared range (photomodulation Fourier transform infrared spectroscopy) is described in detail. It is shown that phase correction plays a decisive role in such measurements. Original results demonstrate the capabilities of this method in a wide wavelength range.