A highly sensitive procedure is presented for the determination of ultra-trace concentration of molybdenum by catalytic adsorptive stripping voltammetry. The method is based on adsorptive accumulation of the molybdenum (Mo)-pyrocatechol violet (PCV) complex on to a hanging mercury drop electrode, followed by reduction of the adsorbed species by voltammetric scan using differential pulse modulation. The reduction current is enhanced catalytically by chlorate. The influence of variables was completely studied by factorial design analysis. Optimum analytical conditions for the determination of molybdenum were established. Molybdenum can be determined in the range 1.0 × 10 −3–100.0 ng ml −1 with a limit of detection of 0.2 pg ml −1. The influence of potential interfering ions on the determination of molybdenum was studied. The procedure was applied to the determination of molybdenum in mineral water and some analytical grade substances with satisfactory results.