The vinoxide anion was selected as a suitable polyatomic since both the anion and neutral are reasonably well characterized. Photodetachment of the anion has been investigated in several experiments, including a SEVI study in our group prior to the installation of cryogenic cooling. The microwave, 148 infrared and electronic spectra of the vinoxy radical and its photodissociation dynamics have also been reported. The electron affinity of vinoxy is 1.825 eV, which is convenient for photodetachment with a dye laser, and the SEVI spectrum exhibits some vibrational structure but is relatively sparse. Quantum chemistry calculations on the vinoxide anion at the B2PLYP-D3/aug-cc-pVTZ level of theory including anharmonicity find two strong infrared transitions, the 4 CO stretch at 1560 cm -1 and the 3 carbonyl CH stretch at 2512 cm -1 . These two modes were thus targeted for our IR cryo-SEVI experiment, with the calculated frequencies taken as starting points for our search. showing a progression in the 9 mode (4 1 0 9 0 𝑛 ), is very similar to the IR-off spectrum, except that the peaks in the IR-on spectrum are shifted to lower eBE by the anion 4 frequency. At larger eBE, however, the IR-on photoelectron spectrum is markedly different, showing FC activity in the 5 and 8 modes, which are not observed in the IR-off spectrum. A harmonic Franck-Condon simulation (Figure ) assuming all anions are in the 4=1 level simulates the IR-on spectrum very well. This agreement shows vibrational excitation of the anion 4 mode remains "in place" on the timescale of our experiment (10 ns) and is well described within the harmonic approximation typically used for the interpretation of photoelectron spectra.