Rapid urbanization has inevitably raised challenges by indirectly adding industry waste to the environment. This problem becomes even more severe when contamination of consumable water is considered. As a leading sector in semiconductor‐related research to face such challenges, gallium oxide and its derivatives have shown remarkable performance by exhibiting controlled, recyclable photocatalytic activities. This work demonstrates the enhancement of the photocatalytic performance of β‐Ga2O3, which is related to the structural and morphological variation induced by rGO wrapping. Firstly, the Ga2O3 nanostructures are obtained by calcinating gallium oxide hydroxide (GaOOH), which is synthesized via a simple chemical route. On the other hand, rGO wrapped β‐Ga2O3 is synthesized using in‐situ hydrothermal treatment. In addition to traditional characterizations such as X‐ray diffractometry (XRD), field emission scanning electron microscopy (FESEM), high‐resolution transmission electron microscopy (HRTEM), Raman spectroscopy, etc., the photocatalytic performance of both pristine and composite systems is studied by time‐dependent UV–Vis absorption spectrum for the degradation of different organic toxic pollutants. It is observed that the composite sample exhibited a larger effective surface area and enhanced optical absorption in the UV–Vis range as compared to the pristine gallium oxide sample. Under UV light irradiation, the rGO wrapped β‐Ga2O3 nanobars can degrade rhodamine B dye entirely within 25 min and exhibit a higher photodegradation rate of 0.1598 min−1 which became 3.5 times higher as compared to that of pure gallium oxide. [ABSTRACT FROM AUTHOR]