Herein we investigate sodium, magnesium, zinc, titanium, silver and thallium complexes based on the perfluorinated trityl alcohol (C6F5)3COH (1) with respect to their structural motifs. The coordination compounds were prepared by alkane or salt elimination reactions in non-polar solvents. XRD analysis revealed a monomeric structure for Ti[OC(C6F5)3]2[OCH(CH3)2]2 (2), dimers for [Mg(OC(C6F5)3)2]2 (3), [Zn(OC(C6F5)3)Et]2 (4) and [Tl(OC(C6F5)3)]2 (5) as well as tetrameric structural motifs for the homoleptic sodium and silver compounds with the general formula [M(OC(C6F5)3)]4: A distorted [NaO]4 cube is observed for [Na(OC(C6F5)3)]4 (6) whereas [Ag(OC(C6F5)3)]4 (7) exhibits a planar [AgO]4 square. Metal fluorine contacts play an important role in all molecular structures presented herein.