Molecular dynamics was applied to study the solvent effects on the molecular self-assembly of a model compound tetrolic acid (TTA) in four different solvents and implications on the polymorph formed during crystallization. TTA has two polymorphic forms (form I and form II) and a solvate form, which are known to form from chloroform, ethanol and dioxane respectively. A hypothesis in literature states that there is a link between the solution chemistry and the solid state polymorphic outcome: the most stable motif (growth synthon) in the solution has the highest probability of crystallizing into the crystal as the structural synthon. This link hypothesis was investigated using molecular simulations in our study. Our results suggest that the strong interactions between TTA and solvent molecules (ethanol or dioxane) prevent the formation of a carboxylic acid dimer in solution and thus promote the crystallization of TTA in a catemer based form or a solvate form. However weak interactions between TTA and solvent molecules (carbon tetrachloride or chloroform) facilitate the formation of carboxylic acid dimers in solution and thus promote the crystallization of a dimer based crystal. Detailed solvent structure plays an important role in determining the relative stability of various growth synthons in solution and also the barriers along the pathway connecting them. Moreover, a procedure to study the solvent-solute interactions in solution and the initial solvent screening for the desired polymorph is proposed, a procedure which can be extended easily to other polymorphic systems.