Core-shelled electrospun nanofibers (ENFs) comprising of a polyvinyl acetate (PVA) shell encapsulating a composite of polyaniline (PANI), tetra-4-(3-oxyflavonephthalocyaninato)cobalt(II) (CoPc-flav), carboxylic acid functionalized multiwalled carbon nanotubes (f-MWCNTs) and an annealed conductive top layer of Nafion (Nf) were used to fabricated a chemically modified gold electrode (Au|ENFs-1-Nf) via the adsorption method. The electrocatalytic sensing capabilities of the Au|ENFs-1-Nf electrode towards Pb(II) ions were evaluated. In comparison to the bare gold electrode and other chemically modified electrodes (CMEs), the Au|ENFs-1-Nf electrode was less prone to fouling showing more stable analyte signal and less compromised background electrolyte currents. The Au|ENFs-1-Nf electrode could detect the Pb(II) cations in a reproducible manner ranging from 8 to 125 μM where limits of detection and quantification of 0.51 and 1.55 μM were obtained, respectively. The analytical performance of the aforementioned CME rendered a comparable percentage recovery (103 %) with that of Inductively coupled plasma-optical emission spectroscopy (ICP-OES) (115 %).