This work addresses photocatalytic oxidation for indoor air purification and more especially the key and realistic issue of VOC mixture treatment. The VOC mixture effect needs to be investigated since indoor air contains several tens of VOCs which may impact photocatalytic oxidation performances. In order to be closer to realistic conditions, concentrations in the ppb range were used and toluene, decane and trichloroethylene (TCE) were treated first as single compounds, then as an equimolar ternary mixture under the same experimental conditions. In a 120 L batch reactor, VOC removal kinetics, reaction inter-mediates and CO 2 mineralization are addressed using dedicated analytical devices compliant with typical ppb level monitoring. Regarding removal kinetics, the mixture effect affects the three VOCs. Regarding toluene and decane removal kinetic, the mixture effect is evidenced as mostly equivalent to a concentration effect, however TCE kinetic is further impacted. From the reaction intermediate point of view, the accurate monitoring of transiently produced intermediates evidences for the first time cross-reactivity between reaction intermediates originating from different primary VOCs. This phenomenon leading to novel reaction intermediate is mostly induced by chlorinated species produced by TCE degradation but remains moderate. An increase in VOC initial concentration to upper ppb levels emphasized a sequential degradation of primary VOC which may be related to competitive adsorption even on such a low concentration range. Finally, even if the mixture effect delays the removal of the primary VOCs, mineralization is slightly modified and, unlike formerly reported experiments on ppm range, final mineralization rates are equivalent under single or mixture condition at ppb levels. This work highlights the fact that photo-catalytic treatment of VOC mixtures cannot be directly extrapolated from single VOC behaviour even at ppb level.