Unique interfacial properties of 2D materials make them more functional than their bulk counterparts in a catalytic application. In the present study, bulk and 2D graphitic carbon nitride nanosheet (bulk g-C3N4 and 2D-g-C3N4 NS) coated cotton fabrics and nickel foam electrode interfaces have been applied for solar light-driven self-cleaning of methyl orange (MO) dye and electrocatalytic oxygen evolution reaction (OER), respectively. Compared to bulk, 2D-g-C3N4 coated interfaces show higher surface roughness (1.094 > 0.803) and enhanced hydrophilicity (θ ∼ 32° < 62° for cotton fabric and θ ∼ 25° < 54° for Ni foam substrate) due to oxygen defect induction as confirmed from morphological (HR-TEM and AFM) and interfacial (XPS) characterizations. The self-remediation efficiencies for blank and bulk/2D-g-C3N4 coated cotton fabrics are estimated through colorimetric absorbance and average intensity changes. The self-cleaning efficiency for 2D-g-C3N4 NS coated cotton fabric is 87%, whereas the blank and bulk-coated fabric show 31% and 52% efficiency. Liquid Chromatography-Mass Spectrometry (LC-MS) analysis determines the reaction intermediates for MO cleaning. 2D-g-C3N4 shows lower overpotential (108 mV) and onset potential (1.30 V) vs. RHE for 10 mA cm−2 OER current density in 0.1 M KOH. Also, the decreased charge transfer resistance (RCT = 12 Ω) and lower Tafel's slope (24 mV dec−1) of 2D-g-C3N4 make it the most efficient OER catalyst over bulk-g-C3N4 and state-of-the-art material RuO2. The pseudocapacitance behavior of OER governs the kinetics of electrode-electrolyte interaction through the electrical double layer (EDL) mechanism. The 2D electrocatalyst demonstrates long-term stability (retention ∼94%) and efficacy compared to commercial electrocatalysts.