The successful synthesis of silver incorporated Fe3O4–rGO ternary nanocomposite for the accurate detection of toxic phenolic isomeric compounds by electrochemical sensing along with self-cleaning ability of photo degradation of the organic dirts is described in this paper. The salient feature of this work is the high sensitivity of the synthesized sensor up to the nanomolar level. The detection limit of the phenolic isomeric compounds such as hydroquinone and catechol are found to be 37.5 nM and 335.4 nM respectively. The synthesized nanohybrid possessing large surface area and mesoporosity also aims to the effective photodegradation of various industrial acidic and basic dyes which may impair electrochemical sensing nature. The photo degradation capacity of the ternary composite was studied and found that a high reduction percentage of above 95 is obtained for these toxic industrial dyes. The dual applications of the ternary nanohybrid as an efficient electrochemical sensor with better photocatalytic self-cleaning property opened a new platform in the various analytical and industrial fields.