The influence of electron and hole scavengers in the photocatalytic digestion of organic matter in the presence of suspended particles of TiO2 was investigated. The process, aiming at the electrochemical determination of traces of heavy metals in water samples, was followed through the recovery of the voltammetric wave of Cd(II) in the presence of EDTA, chosen as model ligand that mimics the complexing effect of natural dissolved organic matter. The accelerating power of O2, acting as electron scavenger, was confirmed. In the absence of O2, a similar function is played by nitrate ions but not, as it seems, by the analyte, Cd(II). On the other hand, CH3OH exhibits an antagonist effect as hole scavenger. This observation may explain why the acetate (from the pH buffer), used to control the medium acidity, leads to a certain reduction in the photocatalytic yield.