The electrochemical behavior of nicotinamide was studied at a carbon paste electrode and the electrodes modified with macrocyclic compounds using voltammetric and impedance measurements. The electrodes so formed were able to bind nicotinamide ions chemically and gave better voltammetric responses than the unmodified ones. The macrocycles used as modifiers for the electrode preparation were 18-crown-6, dicyclohexano-18-crown-6, dibenzo-18-crown-6, 7,16-dibenzyl-1,4,10,13-tetraoxa-7,16-diazacyclooctadecane, 1,4,7,10,13,16-hexathiacyclooctadecane (Hexathia), 1,4,7,10-tetratosyl-1,4,7,10-tetraazacyclododecane, 1,4,8,11-tetraazacyclooctadecane, c-Methylcalix[4]resorcenarene and calix[8]arene. Among these macrocyclic modified electrodes, hexathia showed more affinity towards nicotinamide and a 2.3-fold increase in voltammetric signal was obtained. Impedance measurement was used to confirm this enhancement observed on modified electrode. This increase in anodic peak current was then used for finding linear working range, which was 0.1-500 mu g mL(-1) with a detection limit of 0.03 mu g mL(-1) by DPV. Interference from other vitamins like thiamine HCl (Vit. B-1), riboflavin (Vit. B-2), pyridoxine HCl (Vit. B-6) cynocobamine (Vit. B-12), para-aminobenzoic acid (PABA) and ascorbic acid (Vit. C) was also studied. The modified electrode could be used for the simultaneous determination of riboflavin, nicotinamide and pyridoxine HCl. It has also been utilized for the analysis of nicotinamide in pharmaceutical preparations.