Dimethyl carbonate (DMC) is evaluated as a green, non-deuterated solvent for ¹H NMR spectroscopy using benchtop instrumentation. Its favourable environmental profile, low cost, and spectral simplicity—characterised by a single, easily suppressible signal—make it a promising alternative to traditional deuterated solvents such as CDCl₃. Using WET suppression techniques, high-quality spectra were obtained for a diverse set of compounds, including aromatic aldehydes, phenols, alkaloids, carboxylic acids, and terpene alcohols. DMC also proved effective for reaction monitoring and mixture analysis, enabling direct NMR assessment of pharmaceutical formulations, food products, and synthetic transformations. Its minimal residual signal facilitates integration with chemometric methods, as demonstrated in the classification of edible oils. Sustainability metrics, including Eco-Scale and AGREE scores, highlight the environmental and operational advantages of DMC-based NMR over conventional high-field approaches. These findings demonstrate the feasibility of adopting DMC as a sustainable solvent for lipophilic samples, highlighting its effective performance in modern benchtop NMR spectrometers and reinforcing its potential to drive the transition towards greener analytical practices.