Microstructured fibers offer the possibility of being filled with unconventional materials in order to influence the propagation properties in an optical fiber waveguide. We have studied the filling of microstructured silica fibers with electro-optic polymers. For this purpose a new electro-optic polymer formulation has been developed which is well suited for the complete filling of capillaries in microstructured optical fibers. Such filling could be of special interest for all-solid bandgap fibers thanks to the high refractive index of electro-optic polymers compared with silica, for fiber integrated electro-optical modulation, or for tunable fiber Bragg gratings. We demonstrate waveguiding with such filled fibers, investigate the integration of electrodes for poling and prove the possibility of long-period grating inscription in such fibers.