VUV photoabsorption spectrum of dimethyl carbonate in the energy region 7–11 eV and its complete spectral analysis with the aid of quantum chemical calculations is reported for the first time. The spec- trum recorded using synchrotron radiation comprises of weak bands overlapping a broad intense con- tinuum. With a view to interpret possible vibronic structure, gas phase infrared spectrum in the region 50 0–40 0 0 cm −1 is revisited. Density functional theory (DFT) and time dependent DFT (TDDFT) method- ologies are used to obtain ground state geometry, vibrational frequencies and vertical excitation energies of dimethyl carbonate. The intense broad features in the spectrum could be attributed to valence transi- tions. Based on quantum defect calculations, energy ordering and symmetry, weak bands are designated as ns, np and nd type Rydberg transitions converging to the first five ionization potentials. The highest occupied molecular orbital is nonbonding in nature and largely localized on the oxygen atom of carbonyl group and quantum defect values obtained are consistent with excitation from oxygen lone pair. Excellent correlation is obtained between theoretically predicted (CAM-B3LYP levels of theory) and experimentally observed excited state energies. Potential energy curves of ground and first few excited states generated with a view to provide additional insights into their nature and further describe the observed spectra. The present study provides a comprehensive experimental and computation analysis of the VUV pho- toabsorption spectroscopy of dimethyl carbonate.