The VUV photoabsorption spectra of CHCl₃ and CDCl₃ in the energy region 6.2–11.8eV (50,000–95,000cm⁻¹) have been investigated using synchrotron radiation from the Indus-1 source. Rydberg series converging to the first four ionization limits at 11.48, 11.91, 12.01 and 12.85 eV corresponding to excitation from the 1a₂, 4a₁, 4e,3e, orbitals of CHCl₃ respectively are identified and analyzed. Quantum defect values are observed to be consistent with excitation from the chlorine lone pair orbitals. Vibrational progressions observed in the region of 72,500–76,500 cm⁻¹ have been reassigned to ν₃ and combination modes of  ν₃ + ν₆  belonging to the 1a₂→4p transition in contrast to earlier studies where they were assigned to a ν₃ progression superimposed on the 3e-4p Rydberg transition. The assignments are further confirmed based on isotopic substitution studies on CDCl₃ whose VUV photoabsorption spectrumis reported here for the first time. The frequencies of the ν₃ and ν₆ modes in the 4p Rydberg state of CHCl₃ (CDCl₃) are proposed to be ~454 (409)cm⁻¹ and ~130(129)cm⁻¹ respectively based on the vibronic analysis. DFT calculations of neutral and ionic ground state vibrational frequencies support the vibronic analysis. Experimental spectrum is found to be in good agreement with that predicted byTDDFT calculations. This work presents a consolidated analysis of the VUV photoabsorption spectrum of chloroform.