Conductive polymer hydrogels, which synergize the advantageous features of hydrogels and conductive materials, have been utilized in many electrochemical energy storage applications. Here, we introduce phytic acid as (1) a dispersing agent for pristine multi-walled carbon nanotubes (MWNTs) in aqueous solution containing aniline and as (2) a gelator to form polyaniline (PANI)-based hydrogels after polymerization. The PANI-based hydrogels exhibit nanowire-based mesoporous networks with high surface area and electrical conductivity. The nanostructured core (MWNT)–shell (PANI) hydrogels show an improvement on the electrical conductivity from 0.21 to 1.54 S cm−1 as the loading of MWNTs increases from 0 to 5.0 wt%. The conducting nanowire-based networks with MWNT loadings of 3.0 wt% in the hydrogel provide efficient electron transport pathways that exhibit a maximal specific capacity of 609 F g−1. The scalable and facile synthesis demonstrates excellent electrochemical performance, rendering it attractive for sensing, energy conversion, and energy storage applications.