We present the preparation and investigation of a fluorine‐free surface‐active bis‐N‐heterocyclic carbene (NHC) platinum(II) complex — trans‐[Pt(mPEG3C8Im)2Cl2] — for interface‐enhanced supported ionic liquid phase (SILP) catalysis within a group of (mPEGn)‐substituted ionic liquids (ILs) ([(mPEGn)2Im][A] ILs). The complex was characterized by means of single‐crystal X‐ray diffraction (scXRD) analysis and multinuclear (1H, 13C, 195Pt) NMR spectroscopy, indicating the presence of two almost equimolar syn–anti rotamers of the square‐planar complex in solution. Angle‐resolved X‐ray photoelectron spectroscopy (ARXPS) revealed pronounced interface‐accumulation of trans‐[Pt(mPEG3C8Im)2Cl2] in IL solutions of [(mPEG2)2Im][A] (A− = I− and PF6−).