Two novel cycloplatinated complexes that differ by the presence/absence of a lateral fused cyclopenteno ring, respectively, were prepared. Although contributing to only a few percentage of the whole molecular volume, the presence of this aliphatic protuberance appears to be essential for the emergence of liquid crystalline behaviour. This pair of two similar compounds, non-mesomorphic complex and mesomorphic complex, was prepared as a model to assess the possible link of the self-aggregation in solution with the appearance of the liquid crystallinity in molten state. NMR dilution studies in CDCl3 solution and X-ray diffusion study in neat films show qualitative similarity of the aggregated structures formed by liquid crystalline complex. Solution studies may therefore be a useful additional tool to the characterization of the liquid crystalline properties and other self-association processes of Pt(II) complexes.