A series of molecular complexes of fullerenes C60 and C70 with metal diethyl dithiophosphates [M(dedtp)2]·[C60(70)]3 (1–4), in which M = NiII, CoII, and VIVO was obtained as single crystals and structurally characterized. The complexes exhibit unusual three-dimensional packing of the fullerenes in which each fullerene molecule forms van der Waals contacts with ten fullerene neighbors. Such fullerene packing has been observed for the first time in the molecular complexes of fullerenes. Each metal diethyl dithiophosphate molecule is surrounded by eight fullerenes and forms short van der Waals C···C contacts with fullerenes by ethoxy groups only. Central PS2MS2P fragments of [M(dedtp)2] do not form short van der Waals contacts with fullerenes in 1–4 in contrast to previously studied fullerene complexes with metal diethyldithiocarbamates in which effective π–π interactions between the planar NCS2MS2CN fragments of dithiocarbamates and fullerenes was found. Both [NiII(dedtp)2] in 1 and 2 and [CoII(dedtp)2] in 3 have square-planar environments around the metal center with the M–S bonds in the 2.227(1)–2.275(1) Å range, whereas vanadium atoms have a square-pyramidal environment in [VIVO(dedtp)2] (4) with one short V–O bond that is 1.597(1) Å long and four longer V–S bonds in the 2.394–2.439(2) Å range.