Anthracene-9-carboxylic acid (HL) with a large conjugated π-system and rich optical properties has been used as a primary ligand to prepare tin(IV) complexes with high optical properties. To control and modify the optical properties of prepared compounds, bipyridyl-based ligands with different π-conjugation lengths as ancillary ligands have been employed in the structure of prepared compounds. The results of spectroscopic data and structural analyses showed that all prepared complexes have similar structures. In solid-state, they consist mainly of two components, a complex anion, [(SnCl3)2(L)(OCH3)2]−, which is alike in all complexes and a cation that has not been coordinated to the tin atoms and acted as counter ions and protonated for charge balance. The only variable factor in the structure of compounds is the length of conjugated π-system of bipyridyl ligands. The investigation of the optical properties of prepared compounds showed that the nature and the length of conjugated π-system of ancillary ligands has a pronounce effect on the optical properties of this class of complexes.