T o study reactions occurring on timescales faster than N 10-&lo-3 s, simple mixing of reagents is too slow and other methods of initiating reactions have to be used. Pulses of thermal energy, light quanta or ionising radiation have been used to perturb chemical and biological systems from equilibrium. Pulse radiolysis is the more recent of these three methods of initiating fast reactions, and this review emphasises the versatility of this technique for studying events occurring between 10-11 and 1 0 2 s after energy absorption. The extent and tiniescale of radiation damage in dilute aqueous solutions are outlined and the facile manipulation of experimental conditions to isolate a single reactive species is illustrated. The basic requirements for the radiation pulse and detection system are discussed. T h e experimental techniques which have been used to monitor fast reactions following pulse radiolysis include optical absorption spectroscopy and light scattering, and timeresolved electrical conductivity, polarography, and electron spin resonance spectroscopy. Some applications of pulse radiolysis to study fast reactions of biologically important molecules are illustrated, including the kinetics and thermodynamics of redox processes and electron-transfer reactions, enzymic processes and structural effects which are revealed by physical or kinetic properties.