A home-made vacuum ultraviolet photoionization time-of-flight mass spectrometer has been developed and coupled to an atmospheric simulation chamber operated at atmospheric pressure and to a fast flow tube at low pressure (1–10 Torr). Gas sampling from the simulation chamber is realized directly via a capillary effusive beam, and sampling from the flow tube is via a continuous molecular beam inlet. Both devices are connected simultaneously to the ionization chamber of the mass spectrometer and can be switched in-between within minutes to study gas-phase radical reactions of atmospheric interest in a large range of reaction conditions and reaction times (from milliseconds in the flow tube to hours in the simulation chamber). A cage-shaped photoionization source combined with a commercial 10.6 eV krypton lamp has been developed to provide a high ion collection efficiency along the long light path in the cage. This way, a multiplexed detection with high sensitivity down to the sub-parts per billion volume concentration range, e.g., a limit of detection of 0.3 ppbv with an accumulation time of 60 s for benzene and 1.3 ppbv for the methyl radical, is obtained. The performance and suitability of the setup are illustrated by the study of the chlorine-initiated oxidation reaction of toluene in the atmospheric simulation chamber and in the fast flow tube. Stable products and reactive intermediates have been well-determined and their reaction dynamics are discussed.