Herein, the synthesis and characterization of dicationic dichalcogenide compounds [(SIPr)E]2(OTf)2 (3a‐E) (E = S, Se, Te) based on a saturated N‐heterocyclic carbene (NHC), SIPr [SIPr = C{N(Dipp)CH2}2, Dipp = 2,6‐iPr2C6H3] are reported. Treatment of SIPr (1a) with elemental chalcogens affords the heavier ketone derivatives (SIPr)E (2a‐E), which readily undergo oxidative E–E coupling reactions with triflic anhydride to yield the corresponding products 3a‐E. Compounds 3a‐E are air‐stable crystalline solids and were characterized by NMR and UV/Vis spectroscopy as well as by X‐ray diffraction methods.