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Hybridization of poly(luminol) (PLM) and poly(neutral red) (PNR) has been successfully performed and further enhanced by a conductive and steric hybrid nanotemplate using graphene oxide (GO) and multi-walled carbon nanotubes (MWCNTs). The morphology of the PLM–PNR–MWCNT–GO mycelium-like nanocomposite is studied by SEM and AFM and it is found to be electroactive, pH-dependent, and stable in the electrochemical system. It shows electrocatalytic activity towards NADH with a high current response and low overpotential. Using amperometry, it has been shown to have a high sensitivity of 288.9 μA mM?1 cm?2 to NADH (Eapp. = +0.1 V). Linearity is estimated in a concentration range of 1.33 × 10?8 to 1.95 × 10?4 M with a detection limit of 1.33 × 10?8 M (S/N = 3). Particularly, it also shows another linear range of 2.08 × 10?4 to 5.81 × 10?4 M with a sensitivity of 151.3 μA mM?1 cm?2. The hybridization and activity of PLM and PNR can be effectively enhanced by MWCNTs and GO, resulting in an active hybrid nanocomposite for determination of NADH.