Picosecond and nanosecond time-resolved resonance Raman spectra of the intramolecular charge transfer (ICT) and triplet state of DMABN-d4 have been obtained over the frequency range from 650 to 2250cm−1. The spectra and the isotopic shifts observed on going from normal DMABN to the ring deuterated analogue are interpreted with the aid of DFT vibrational analysis of ground state spectra and comparisons made with closely related compounds. The data confirm our previous results but the isotopic shifts induced by the ring deuteration provide additional evidence clarifying the planar structure of the triplet state and indicating full localisation of negative charge on the cyano group.