In this work, the influence of the reactor configuration and the characteristics of the catalysts on the photodegradation of trichloroethylene (TCE) vapors are studied under sunlight illumination. The photocatalytic activity tests were carried out using two types of continuous flow reactors: (i) a compound parabolic collector (CPC) and (ii) a simple flat reactor. Three different photocatalysts based on were utilized: (i) commercial powders calcined at (ii) a sample synthesized by treating the commercial sample at in an gas flow, and (iii) thin film coatings on differently shaped borosilicate glass supports prepared by a sol-gel procedure. The obtained data reveal that the photonic efficiency for the removal of TCE is quite high but slightly decreases with increasing the light intensity. The commercial sample presents the highest efficiency while nitrogen doping seems to be slightly detrimental for photoactivity, despite the fact that certain photoresponse in the visible can be envisaged. In contrast, transparent sol-gel coatings present the highest TCE degradation rate per mass of catalyst. Regarding the type of reactor, it is found that the use of CPCs can be advantageous, especially when dealing with high volumes of effluent and elevated concentration of TCE, although flat reactor also shows a considerable efficiency.