The technical feasibility and performance of photocatalytic degradation of four water-soluble pesticides (diuron, imidacloprid, formetanate and methomyl) have been studied at pilot scale in two well-defined systems of special interest because natural-solar UV light can be used: heterogeneous photocatalysis with titanium dioxide and homogeneous photocatalysis by photo-Fenton. The pilot plant is made up of compound parabolic collectors (CPCs) specially designed for solar photocatalytic applications. Experimental conditions allowed disappearance of pesticide and degree of mineralisation achieved in the two photocatalytic systems to be compared. In order to assure that the photocatalytic results are consistent, hydrolysis and photolysis tests have been performed with the four pesticides. The initial concentration tested with imidacloprid, formetanate and methomyl was 50 and 30 mg/l with diuron, and the catalyst concentrations were 200 mg/l and 0.05 mM with TiO2 and iron, respectively. Total disappearance of the parent compounds and 90% mineralisation have been attained with all pesticides tested, methomyl being the most difficult to be degraded with both treatments. First-order rate constants, initial rate, time necessary for mineralising 90% of the initial TOC and hydrogen peroxide consumption were calculated in all cases, enabling comparison both of treatments and of the selected pesticide reactivity.