This study has been divided into four chapters. Chapter 1 gives a general introduction of high performance polymers, the history and development of electrochromism, nanostructures in electrochromism, and organic-inorganic hybrids. In chapter 2, porous polyamide hybrid films were prepared to investigate the synergistic effect of porous structure and organic-inorganic hybrids toward electrochromic (EC) behaviors. Porous structure produced by the electrolyte and hybrid content through sol-gel reaction with metal oxide had been shown to enhance EC properties in different mechanisms: the former provides channels for counter-ions to diffuse in and out of the film more easily, and the latter offers an electron-storage group that can assist charge transferring during the redox process. Therefore, by combining both of the modifications, a more advanced EC performance is expected to be obtained. In chapter 3, pentiptycene structure is introduced to the polymer chain. There are V-cavities and U-cavities in the scaffold of pentiptycene, which form the internal molecular free volume (IMFV). The free volume it caused may be analogue to the porous structure, implying that pentiptycene could give a positive effect on the EC properties. Though the pentiptycene used in this study was not electrochromic, if the structure was combined with EC centers, the material would be very promising. Finally, all the results are concluded in Chapter 4.