Biomass-templated spinel ferrite/carbon nanocomposites are promising electrode materials; however, dense carbon shells formed during low-temperature carbonization can block electrolyte access to active sites and impair electrochemical performance. The role of this carbon-shell passivation in biomass-derived ferrite/carbon composites remains largely unexplored. Here, we identify this limitation in a stepwise-synthesized NiFe₂O₄/rGO@C composite (NFC-S, BET surface area = 5.23 m² g⁻¹, ΔEp = 113.3 mV) and resolve it through a rationally designed one-pot optimization strategy in which urea simultaneously serves as a pore-forming agent and nitrogen precursor. The optimized composite (N-NFC-O) achieves a BET surface area of 186.39 m² g⁻¹—a 35.6-fold enhancement—with 70.1% micropore contribution and 3.13 at.% in-situ nitrogen doping. Electrochemically, ΔEp narrows to 72.3 mV and enables efficient NO₂⁻ oxidation with a ~70 mV cathodic shift, whereas NFC-S shows negligible catalytic response under identical conditions. As a proof of concept, differential pulse voltammetry (DPV) yields a nitrite sensitivity of 9.17 µA cm⁻² mM⁻¹ and a detection limit of 92.5 µM. Overall, this work identifies carbon pore accessibility as a key structural descriptor governing electrocatalytic performance in biomass-derived ferrite/carbon composites and provides a general design strategy for developing high-performance biomass-derived carbon/oxide hybrid electrodes.