In the field of miniaturized devices one of the basic but unreciprocated problems is the instability induced dewetting in polymer thin films. The significance of choosing solvents for deconstructing polymer thin films along with their stability is investigated by rinsing supported polystyrene thin films on silicon wafer with native oxide in four different solvents, such as toluene, chloroform, tetrahydrofuran, and acetone. The solvents are chosen according to their relative energy difference with the polymer. The remnant thickness and morphology of the residual polymer subject to solvent rinsing are characterized. Fine tuning of rinsing time leads to a progressive decrement of film thickness that allows the investigation of stability of the residual film resulting from different solvent leaching. The stability of these films is found to be dependent on various interactions involved in the system such as van der Waals dispersive forces, steric repulsions, acid-base interactions, etc. Based on these solvent-specific parameters, the residual films undertake spinodal dewetting at different time scale of rinsing. The experimentally observed solvent specific transition thickness where residual films undergo spinodal dewetting is weighed against theoretical calculations covering all these interactions. It is shown that the solvent polarity is an important factor in provoking the instability of rinsed films. In particular, films rinsed with a polar solvent exhibit an earlier dewetting (i.e., higer transition thickness value) than those rinsed with a nonpolar solvent. © 2016 American Chemical Society.