A self-assembly directed approach was adopted to modify glassy carbon electrode (GC) with gold nanoparticles incorporation and the electrocatalytic performance of self-assembly modified electrode, GC/SA-Au-ME was critically evaluated for the oxidation of ascorbic acid (AA). The modification involves the dispersion of multi-wall carbon nanotube (MWNT) and an inclusion complex, beta-cyclodextrin-4-aminothiophenol on the surface of GC electrode in the presence of cetyltrimethylammonium bromide (CTAB). Gold nanoparticles were deposited into the self-assembled sites to fabricate the modified electrode, GC/SA-Au-ME. Another electrode (GC-Au-ME) was fabricated under similar conditions in the absence of CTAB. The electrocatalytic activity of the modified electrodes (GC/SA-Au-ME and GC-Au-ME) towards the oxidation of AA was critically compared. Cyclic voltammetry, chronoamperometry, and double potential chronoamperometry were used to evaluate the characteristics of the modified electrodes. The self-assembled electrode (GC/SA-Au-ME) shows excellent electrocatalytic activity over the other electrode, GC-Au-ME. Augmented current response, faster electron transfer kinetics (with a rate constant for electron transfer process as 3.25 x 10(4) cm3 mol(-1) s(-1)), linear range of response for the analyte (1-50 mM with an extended detection limit to 1 microM), better sensitivity, and selectivity were witnessed for the self-assembly directed modified electrode.