In this study, a TiO₂/(MA)₂SnCl₄ nanocomposite film was synthesized using a sustainable, sunlight-driven approach, demonstrating enhanced photocatalytic performance for environmental remediation. TiO₂ nanoparticles (TiO₂-NPs) were dispersed in ethanol and mixed with a methylammonium (MA) and SnCl₂ precursor solution, followed by drop-casting onto a glass substrate and exposure to direct sunlight for 2 h. Sunlight served as an energy source, facilitating in situ structural modifications and leading to the formation of a well-integrated TiO₂/(MA)₂SnCl₄ hybrid structure, where TiO₂ was effectively encapsulated. Characterization revealed a band gap reduction from 3.1 eV (TiO₂-NPs) to 2.6 eV in the nanocomposite, extending light absorption into the visible range. The formation of Sn–O–Ti interactions enhanced charge separation, minimized electron–hole recombination, and improved charge carrier dynamics. Photocatalytic degradation tests using methylene blue (MB) under sunlight showed that the nanocomposite film achieved 90% MB degradation within 60 min, outperforming TiO₂-NPs, which achieved only 75% degradation. The presence of oxygen vacancies (OVs) generated during sunlight exposure further enhanced photocatalytic efficiency by acting as charge traps and reaction sites. This study introduces a green synthesis strategy leveraging sunlight as a renewable energy source, marking the first integration of (MA)₂SnCl₄ with TiO₂-NPs for enhanced photocatalysis. The synergistic effects of extended visible-light absorption, defect engineering, and efficient charge separation make TiO₂/(MA)₂SnCl₄ nanocomposite films a scalable, cost-effective solution for water purification applications, offering a promising solar-driven approach to addressing global water contamination challenges.