Photoplethysmography (PPG) is a simple and low-cost optical technique that can be used to detect blood volume changes in the microvascular bed of tissue. It is often used non-invasively to make measurements at the skin surface. The PPG waveform comprises a pulsatile ('AC') physiological waveform attributed to cardiac synchronous changes in the blood volume with each heart beat, and is superimposed on a slowly varying ('DC') baseline with various lower frequency components attributed to respiration, sympathetic nervous system activity and thermoregulation. Although the origins of the components of the PPG signal are not fully understood, it is generally accepted that they can provide valuable information about the cardiovascular system. There has been a resurgence of interest in the technique in recent years, driven by the demand for low cost, simple and portable technology for the primary care and community based clinical settings, the wide availability of low cost and small semiconductor components, and the advancement of computer-based pulse wave analysis techniques. The PPG technology has been used in a wide range of commercially available medical devices for measuring oxygen saturation, blood pressure and cardiac output, assessing autonomic function and also detecting peripheral vascular disease. The introductory sections of the topical review describe the basic principle of operation and interaction of light with tissue, early and recent history of PPG, instrumentation, measurement protocol, and pulse wave analysis. The review then focuses on the applications of PPG in clinical physiological measurements, including clinical physiological monitoring, vascular assessment and autonomic function.