A physical insight regarding poly(tetrafluoroethylene) (PTFE) is revealed herein. The driving force for the oriented growth of materials on aligned PTFE is investigated. The growth has been reported in numerous publications for a wide range of deposited materials on aligned PTFE layers since its discovery in 1991 because it is a promising method for preparing ordered molecular films. MD model simulations demonstrate herein that the shallow charged atomic grooves between adjacent PTFE chains trap typical two linear molecules, thus explaining the remarkable degrees of uniaxial orientation in their deposited thin films on the layers. Charge modifications to the model demonstrate for the first time that the negative charge of its fluorine atoms is crucial for the remarkable degrees. Hence, such an orientation is only possible with PTFE.