This paper presents a conformational analysis of some polyethers containing the oxetanic ring in the main chain. The studied polymers were synthesized by phase transfer catalysis, using 3,3-bis(chloromethyl)oxetane and various bisphenols. The analysis was performed using the Cerius(2) program (version 2.0) molecular simulation software for material science, designed by Molecular Simulations Incorporated (MSI). This study tries to elucidate some aspects concerning the difficulties appearing in the liquid crystalline property’s characterization. These difficulties are induced by the cross-linking processes that take place in certain situations due to the opening of the oxetanic rings at high temperature.