Photocatalysis based on titanium dioxide (TiO
2) has become a promising method to remediate industrial and municipal effluents in an environmentally friendly manner. However, the efficiency of TiO
2 is hampered by problems such as rapid electron–hole recombination and limited solar spectrum absorption. Furthermore, the sensitization of TiO
2 through heterojunctions with other materials has gained attention. Vanadium, specifically in the form of ammonium vanadate ((NH
4)
2V
3O
8), has shown promise as a photocatalyst due to its ability to effectively absorb visible light. However, its use in photocatalysis remains limited. Herein, we present a novel synthesis method to produce lamellar (NH
4)
2V
3O
8 as a sensitizer in a supramolecular hybrid photocatalyst of TiO
2–stearic acid (SA), contributing to a deeper understanding of its structural and magnetic characteristics, expanding the range of visible light absorption, and improving the efficiency of photogenerated electron–hole separation. Materials, such as TiO
2–SA and (NH
4)
2V
3O
8, were synthesized and characterized. EPR studies of (NH
4)
2V
3O
8 demonstrated their orientation-dependent magnetic properties and, from measurements of the angular variation of g-values, suggest that the VO
2+ complexes are in axially distorted octahedral sites. The photocatalytic results indicate that the 2D/2D heterojunction layered TiO
2/vanadate at a ratio (1:0.050) removed 100% of the methylene blue, used as a model contaminant in this study. The study of the degradation mechanism of methylene blue emphasizes the role of reactive species such as hydroxyl radicals (
•OH) and superoxide ions (O
2•−). These species are crucial for breaking down contaminant molecules, leading to their degradation. The band alignment between ammonium vanadate ((NH
4)
2V
3O
8) and TiO
2–SA, shows effective separation and charge transfer processes at their interface. Furthermore, the study confirms the chemical stability and recyclability of the TiO
2–SA/(NH
4)
2V
3O
8 photocatalyst, demonstrated that it could be used for multiple photocatalytic cycles without a significant loss of activity. This stability, combined with its ability to degrade organic pollutants under solar irradiation, means that the TiO
2–SA/(NH
4)
2V
3O
8 photocatalyst is a promising candidate for practical environmental remediation applications.
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