Fabrication and electro-optic applications of glass optical fibers were reviewed. Theoretical description on the electro-optic Kerr effect in glass optical fibers, particularly for the second-order optical nonlinearity was given. Fabrication procedure and the characterization of the nonlinear electro-optic fibers with internal electrodes were described. Several electro-optic devices based on the polarimetric cells made by the nonlinear optical fibers with internal electrodes were also discussed with the experimental results on the electro-optic effect.