The preparation and electrochemical characterization of a carbon paste electrode modified with bis(N,N-piperidinedithiocarbamate)-mu-tris(N,N-piperidinedithiocarbamate)diruthenium(III) complex, alpha-[Ru2(Pip)5]Cl are described. The best voltammetric response was obtained for a 10% (m/m) alpha-[Ru2(Pip)5]Cl content in the paste, potassium acid phthalate solution pH 4.0 as supporting electrolyte and scan rate of 100 mV s-1. The analytical potentialities of the electrode have been evaluated using L-ascorbic acid (vitamin C) as a probe. A sensitive linear voltammetric response for L-ascorbic acid was obtained in the concentration range 4.50-113x10(-5) mol l-1 (7.92-200 mg l-1) with a slope of 1.12x10(4) microA mol-1, and a detection limit (3sigma/slope) of 7.00x10(-6) mol l-1 using cyclic voltammetry. The concentrations of L-ascorbic acid in pharmaceutical formulations (tablets and liquid) were determined using the modified electrode and compared with an iodimetric procedure with good agreement at the 95% confidence and relative error lower than 1%.