Pristine polysilane containing only Si and H is considered as a potential precursor material that allows the solution-based deposition of hydrogenated amorphous Si (a-Si:H) thin-films reducing manufacturing cost of Si thin-film photovoltaic devices. This study explored three different synthetic routes including Würtz-type reductive coupling reaction, hydrogenation of Si anionic compound, and the dehydrocoupling reaction in order to realize the soluble polysilane molecules. While Würtz-type reaction of diiodosilane presented us a direct synthetic scheme for hydrogenated polysilane, the results indicated that an extremely controlled air-free system for the synthesis and sample handling would be necessary to prevent the formation of siloxane bonds from the spontaneous reaction between silane-based molecules and water in the air. While the hydrogenation of CaSi 2 and the dehydrocoupling reaction of phenylsilane provided more stable forms of polysilane, dissolution of the polysilane from CaSi 2 in dichlorobenzene was not successful possibly due to its layered structure succeeded from CaSi 2 and the removal of the phenyl groups from the synthesized polyphenylsilane remains as a challenge to realize the polysilane precursor necessary for the solution-based thin-film process of a-Si:H.