The unique versatility with the tailorable nature was accomplished in the reincarnated hybrid material viz octa functionalized-polyhedral oligomeric silsesquioxane. This wrapped a wide range of applications but lacked significant exploration in the electrochemical sensing field. This prompted the elucidation of the electrochemical sensing activity of octa vinyl functionalized polyhedral oligomeric silsesquioxane (V-POSS) which showed excellent charge transfer ability with driving force for oxidation owing to interfacial potential. A nanocomposite was designed utilizing the distinguished multi-layer graphene (MLG) based carbon allotrope as a conducting matrix. The developed V-POSS: MLG was physiochemically characterized to affirm its formation with regard to supporting the electrochemical performance towards the detection of 2-hydroxy benzophenone (2-HBP). The analyte of interest was chosen because it can cause numerous health hazards and major environmental pollution leading to a loss in biodiversity in the aquatic environment (ng-mg/L accumulation). Hence, the V-POSS: MLG-based sensor was tuned to achieve 0.2 nM detection and 0.66 nM quantification plausibility with the linear dynamic range of 1 nM–100 μM. Also, the constructed sensor was regulated to accomplish detection capability in real water samples followed by cross-validation for precision and reliability of the sensor with the HPLC-UV technique.