Herein, novel hierarchical Gd@WO3 pom-pom-like microstructures have been prepared through the hydrothermal method and combined with RGO sheets (denoted as RGO/Gd@WO3). The synthesized materials, along with their analogs, were characterized through X-ray diffraction (XRD), scanning electron microscopy (SEM), thermogravimetric analysis (TGA), Fourier transform infrared (FT-IR), Mott-Schottky, current-voltage (I-V), electrochemical impedance spectroscopy (EIS), and optical analyses. The unique morphology of pom-pom-like microstructures allowed better interaction with pollutant molecules. Rare earth element (Gd3+) ions act as trapping species for photo-generated electrons and prolong the life span of reactive oxygen species (ROS). The high conductivity and flexible nature of RGO sheets provided fast transport of active species and provided stability to the photocatalytic material. To test the photocatalytic efficiency of RGO/Gd@WO3, crystal violet (CV) and acetylsalicylic acid (ASA) were used as model pollutants. Under a mimetic light source, RGO/Gd@WO3 exhibited maximum photodegradation of 98.8% and 84% for CV and ASA within 120 min of irradiation, respectively. Photocurrent, Mott-Schottky, and EIS experiments proved the production, effective separation, and transmission of photo-active species in the presence of RGO/Gd@WO3 as compared to Gd@WO3 and WO3. Given the electrochemical testing and optical analysis, the photocatalytic mechanism is anticipated for the high photocatalytic activity of RGO/Gd@WO3. The novel RGO/Gd@WO3 photocatalyst proved to be a superior photocatalytic material for the photodegradation of organic pollutants.