Stepwise syntheses of monometallic palladium(II) and bimetallic palladium(II)/platinum(II) complexes were carried out in order to measure the metallophilicity of potential tetradentate bis(alkylthio)ylidenemalonato ligands. The reaction of [Pd](SO4) ([Pd] = (Me4en)Pd; Me4en = N,N,N′,N′‐tetramethylethylenediamine) with Ba[L] {L: bis(methylthio)methylenepropanedioato (1); bis(ethylthio)methylenepropanedioato (2); 1,3‐dithiapan‐2‐ylidene‐malonato (3)} produced [[Pd]‐O,O′‐L]. Successive reactions of [[Pd]‐O,O′‐L] with {M}(NO3)2 ({M} = (en)M; en = ethylenediamine; M = PdII, PtII), followed by anion exchange with PF6–, yielded banana‐shaped bimetallic complexes [[Pd]‐O,O′‐L‐S,S′‐{M}](PF6)2. In case of [[Pd]‐O,O′‐1], the bis(alkylthio)methylene group of 1 was bent strikingly from the palladium square plane (dihedral angle = 78.26°), in contrast to the cases of [[Pd]‐O,O′‐3] (120.84°) and [[Pd]‐O,O′‐L‐S,S′‐{M}](PF6)2 (101.75–103.54°). [[Pd]‐O,O′‐L] (L = 1, 2) in Me2SO existed as a mixture of [[Pd]‐O,O′‐L] and [(Me4en‐N)(Me2SO‐S)‐Pd‐O,O′‐L] in a mol ratio of 1:1. For the labile species, a linkage isomeric equilibrium between [[Pd]‐O,O′‐L] and [[Pd]‐O,S‐L] in D2O was observed. [[Pd]‐O,O′‐3] and [[Pd]‐O,O′‐L‐S,S′‐{M}](PF6)2, however, were found to be inert in Me2SO or D2O. Such notably different solution behavior possibly can be explained by the steric hindrance occurring via the dihedral angles between the palladium square plane and the ylidene moiety. Variable‐temperature 1H NMR spectra of the banana‐shaped bimetallic complexes [[Pd]‐O,O′‐L‐S,S′‐{M}](PF6)2 in CD3CN solution revealed that the amine proton resonances are sensitive to the fluxional motion of the remote bis(alkylthio)ylidene groups, suggesting the occurrence of interconversion between the two “bent‐up” and “bent‐down” forms.