Imines play a fundamental role in organic synthesis and some of them have been detected in space. However, the simplest imines are spectroscopically not well-characterized. Herein we present the infrared and UV/Vis spectroscopic characterization of 2-iminoacetaldehyde using cryogenic matrix isolation techniques. After UV irradiation of 2-azidoacetaldehyde in solid argon at 3 K we identified two conformers of 2-iminoacetaldehyde, which can be photochemically interconverted. Deuterium labelling experiments and high level coupled cluster calculations at the CCSD(T)/CBS level of theory provide further evidence for the formation of 2-iminoacetaldehyde.