Electrochemical oxidation (EO) process is an inexpensive and effective technology for treatment of industrial sewage containing toxic organic pollutants which mainly ascribed to the reactive oxygen species (ROS). The generation of ROS strongly depends upon the microstructure, composition and physiochemical properties of the anodic materials. Nanostructured highly porous 3D–Ti/Sb–SnO2–Gr electrode, based on 3D porous graphene hydrogel is fabricated via a fast-evaporation technique through layer by layer (LBL) deposition. The fabricated 3D porous electrode possesses high oxygen evolution potential (2.40 V), higher porosity (0.90), enhanced roughness factor (181), and larger voltammetric charge value (57.4 mC cm-2). EO of Rhodamine B (RhB) is employed to evaluate the efficiency, the rate constant (k) value of 4.93 10-2 min-1 is obtained which is 3.91 times higher than the traditional Ti/Sb–SnO2. Moreover, the mineralization of 2, 4–DCP by using nanostructured 3D–porous Ti/Sb–SnO2–Gr anode is also investigated. Within 40min of reaction, 99% of removal rate is achieved, meanwhile, 81% of TOC removal is recorded with lowest SECTOC of 62.25 KWh (kg TOC) –1 at maximum MCE% (246%). For understanding the pathway of 2, 4–DCP degradation, the intermediates are tested through HPLC and UPLC/MS-MS, showing a complete mineralization.Furthermore, a simple template removal method has been reported for fabrication of two different kinds of hierarchically porous architectures, Ti/Sb-SnO2-honeycomb (honeycomb) and Ti/Sb-SnO2-network (network) with remarkable porosity and layer by layer arrangement in multiple directions. The honeycomb and network possess high OEP value upto 2.60 V and 2.76 V, with 7.46 mC cm-2 and 11.96 mC cm-2 total voltammetric charge compared to the conventional one (3.0 mC cm-2), which indicates the significant enhancement in electrochemical active sites. The mechanistic study suggests that more electro active sites provided by hierarchically porous electrodes lead to accelerate HO? generation and the channels of porous structure significantly promotes the adsorption and diffusion of pollutant molecules.In addition, high-performance catalyst in terms of reactivity, selectivity with long time activation, noble metal-metal oxide nanocomposites (NMMOs) is synthesized by using micro emulsion technique. Encapsulation of Pt within MOs shell is successfully obtained which simultaneously prevent the direct exposure of NM as well as intimate a 3D contact between NM and MOs is developed which provided larger interfacial interaction leading to strengthen its reactivity. The EO of PFOA is employed to explore the catalytic activity of Pt@MO nanoparticles, and the obtained results showed that PFOA is completely degraded within 6 h while the traditional Pt-MO showed only 20% of degradation. The quantitative measurements of stable intermediates during the mineralization were carried out by UPLC/MS-MS to reveal the complete mineralization as well as the stability was also estimated to figure out its practical usage.All fabricated electrodes demonstrate superior advantages over the traditional once such as better electrocatalytic performance, higher stability, low energy consumption and efficient mineralization of organic water pollutants. It is expected that this work can be a promising approach towards practical usage for recalcitrant pollutant incineration.