Picosecond time-resolved Raman spectra of the intramolecular charge transfer state of DMABN and DMABN-d6, have been obtained in resonance with two different electronic states, using probes at 330 and 400 nm. Fluorescence was rejected using a Kerr gate. Several resonance Raman bands in the 750–2200 cm−1 region are reported for the first time. The prominent CN stretch at 2096 cm−1 and bands sensitive to the amino group deuteration are only observed using the 330 nm probe. At 400 nm, bands assigned to modes localised on the ring dominate the spectrum. The results support the TICT model.