The gold nanorods stabilized in amine-functionalized silicate sol-gel matrix (Au-TPDT NRs) in aqueous medium are prepared and their application toward the electrochemical sensing of reduced beta-nicotinamide adenine dinucleotide (NADH) is demonstrated. The prepared Au-TPDT NRs is characterized by using absorption spectroscopy and transmission electron microscopy. The electrochemical characteristics of the Au-TPDT NRs modified electrode are studied by using cyclic voltammetry. The electrocatalysis and electrochemical sensing of NADH at physiological pH using the Au-TPDT NRs modified electrode are investigated. The amperometric sensing of NADH shows enhanced electrocatalytic activity for the Au-TPDT NRs modified electrode without incorporating any mediator due to the synergetic catalytic effect of Au NRs and TPDT silicate sol-gel matrix. The amperometric current increased linearly with increasing the NADH concentration in the range from 1 to 13 A mu M and the lowest detection limit is estimated as 0.38 A mu M. The present work demonstrates that the GC/Au-TPDT NRs modified electrode is simple to prepare and shows good response for the electrochemical detection of NADH.