An investigation of the photocatalytic degradation of indoor air model pollutants: toluene, n-decane and tri-chloroethylene (TCE), as single contaminants and in a mixture is proposed. The degradation of these contaminants was performed in a continuous closed-loop reactor operating in recirculation mode. Degradations were conducted at ppb level concentrations and under humid conditions (RH = 50%) in order to be closer to real applications of photocatalytic oxidation (PCO) systems developed for indoor air quality improvement. Accurate analytical methods were developed to identify and quantify the majority of the potential formed intermediates. Kinetic constants and the time constant of degradation were obtained for the model pollutants. Under these conditions, the degradation of the three VOCs in a mixture did not really show a decrease in the kinetic rates. Toluene and decane degradations were slightly slowed down when they were in a mixture but no significant interference was demonstrated with TCE. The intermediates formed during the PCO of the mixture of VOCs were the same as those identified during single degradation, leading to the hypothesis of few interactions between them. Only the formation and degradation of secondary intermediates, mostly composed of aldehydes, were time delayed. The total VOC concentration may lead to a competitive adsorption that seemed more sensitive for the last formed oxygenated intermediates. This investigation points out the need to always monitor the last formed aldehyde intermediates. Monitoring acetaldehyde and formaldehyde enables an evaluation of the efficiency and a better design of future PCO systems for indoor applications.