To investigate the effect of "chemical energy" by solvent on structural development, initially molded amorphous poly(ethylene 2,6-naphthalene dicarboxylate) (PEN) films were drawn in various solvent systems and at the optimum temperatures deliberately determined, and the resulting fine structure and properties were analyzed by using several experimental techniques. Water, 1-butanol, 1,4-dioxane/water (20 : 80 by volume), and 1,4dioxane/1-butanol (20 : 80 by volume) were chosen for drawing solvent. For this study, in view of chemical structure and solubility parameter, though, these are nearly immiscible or partially miscible liquids against PEN, with just the plasticizing actions more or less the primary concern here. Interesting enough, the temperature range near the main endothermic peak corresponding to the depressed boiling point of liquid caused by unfavorable interaction between PEN and solvent in mixtures of amorphous PEN film with various solvent systems, as determined by the DSC scans, was found to coincide with the optimum drawable range for each solvent system, over which several experiments, including the determination of maximum draw ratio (DRmax) have been carried out throughout the study. The experimental results obtained from this study could be explained, through qualitatively, in terms of the interactions between PEN and solvents. Hence, it is expected to control the fine structure and properties of PEN films resulting from the low-temperature solvent drawing via a suitable choice of liquids and the corresponding draw temperature ranges. (C) 2003 Wiley Periodicals, Inc.