Herein, we report, for the first time, the preparation, matrix-isolation, and spectroscopic characterization of the methyl selenyl radical and methyl-Se-nitrososelenol in combination with DFT and CASSCF/NEVPT2 computations. The latter proved to be highly photolabile, and upon irradiation with light at λ = 465 nm it leads to methyl selenyl and nitric oxide radical pairs. Upon λ > 730 nm irradiation it rearranges back to methyl-Se-nitrososelenol.