Cleavage of the Se-Se bond in [2-(Et2NCH2)C6H4]2Se2 (1) with SO2Cl2 (1:1 molar ratio) yielded the organoselenium(II) chloride [2-(Et2NCH2)C6H4]SeCl (2). Treatment of 2 with excess of KX yielded the organoselenium(II) halides [2-(Et2NCH2)C6H4]SeX [X = Br (3), I (4)]. The new compounds 2e4 were characterized by solution NMR spectroscopy (1H, 13C, 77Se, 2D experiments). The solid-state molecular structures of 2, 2$HCl and 3 were established by single crystal X-ray diffraction. Distorted T-shaped coordination geometries of type (C,N)SeX (X = Cl, Br) and CSeCl2 were found for the neutral halides 2 and 3, and the zwitterionic species [2-{Et2Nþ(H)CH2}C6H4]SeCl2‾ (2$HCl), respectively. DFT calculations were performed on 2e4 and the related tellurium compounds [2-(Et2NCH2)C6H4]TeX [X = Cl (5), Br (6) and I(7)] in order to elucidate the bond nature and FT-Raman features of this class of organochalcogen(II) derivatives.