A titanium-based zeolitic thiophene-benzimidazolate framework has been designed for the direct synthesis of dimethyl carbonate (DMC) from methanol and carbon dioxide. The developed catalyst activates carbon dioxide and delivers over 16% yield of DMC without the use of any dehydrating agent or requirement for azeotropic distillation. This dataset is associated with the following publication: Varma, R., M. Nadagouda, S. Verma, and R.B.N. Baig. Fixation of carbon dioxide into dimethyl carbonate over titanium-based zeolitic thiophene-benzimidazolate framework. Scientific Reports. Nature Publishing Group, London, UK, issue}: 655, (2017).