Isomerization of 2-chloromalonaldehyde (2-ClMA) is explored giving access to new experimental data on this derivative of malonaldehyde, not yet studied much. Experiments were performed isolating 2-ClMA in argon, neon, and para-hydrogen matrices. UV irradiation of the matrix samples induced isomerization to three open enolic forms including two previously observed along with the closed enolic form after deposition. IR spectra of these specific conformers were recorded, and a clear assignment of the observed bands was obtained with the assistance of theoretical calculations. UV spectra of the samples were measured, showing a blue shift of the π* ← π absorption with the opening of the internal hydrogen bond of the most stable enol form. Specific sequences of UV irradiation at different wavelengths allowed us to obtain samples containing only one enol conformer. The formation of conformers is discussed. The observed selectivity of the process among the enol forms is analyzed.