New compounds Ia–h of the form [(Me2SO)ClPt(HR2DTO κ‐S,S Pt)] (HR2DTO = secondary dithiooxamide, with R = methyl, ethyl, n‐propyl, n‐butyl, n‐decyl, isopropyl, (R)‐1‐phenylethyl, or (S)‐2‐hydroxypropyl; κ‐S,S Pt denotes the coordination of the DTO moiety to the Pt atom) have been prepared and used to synthesize platinum(II)/ferrocene dimetallic species IIa–h of formula [(dppf)Pt(HR2DTO κ‐S,S Pt)]Cl (dppf = 1,1′‐diphosphinoferrocene). Complexes IIa–e, bearing unbranched groups on the dithiooxamide moiety (i.e., R = methyl, ethyl, n‐propyl, n‐butyl, or n‐decyl groups), self‐assemble upon standing to form unprecedented hexameric macrocycles IIIa–e. Compounds IIa–e, IIIa–e, as well as IIf–h, have been characterized by a combination of 1H, 13C, 31P NMR spectroscopy and 2D‐ROESY and diffusion‐ordered NMR spectroscopy (DOSY) experiments; the latter experiments have been used to calculate the hydrodynamic radius of IIa–e and IIIa–e, assisted by the data provided by the X‐ray crystal structure of IIh. Compounds IIIa–e are characterized by the presence of six dppf bridging units occupying the inner rim of the macrocycles and exhibit interesting properties, for example, oxidation of IIIa–e occurs around +0.40 V versus saturated calomel electrode (SCE), whereas oxidation of the type II species occurs at potentials greater than +1.0 V. Oxidation of IIIa–e is explained through a delocalized orbital extending over the six dppf subunits. The reversibility of the self‐assembly process is finally demonstrated by alternate addition of acids and bases to the type III compounds.