Solubility of polysilane macromolecules has so far been a scientific as well as technological problem due to a lack of understanding of their proper molecular size and agglomeration/de-agglomeration conditions. Here we show that, in contrary to previous reports, the polysilane molecules are inherently small enough to be, under right conditions, dissolved. We used a dynamic light scattering and a differential scanning calorimetry to show that even under a dilute regime the polymer molecules are agglomerated at room temperature and undergo de-agglomeration at slightly elevated temperatures of around 40 °C. The de-agglomeration results in formation of stable solutions of the polymer molecules of different topological structure in different organic solvents. We determined the polymer molecular sizes to be around 20 nm, much lower than previously reported. The measured molecular size was confirmed by transmission electron microscope imaging of the individual molecules.