The polarization properties of a new structure of high birefringence polarization maintaining photonic crystal fibers were explored, which were consisted of elliptical-holes and near elliptical core triangle lattice of hexangular structure based on polymer. The optical birefringence and the first order polarization mode dispersion were studied based on a full-vector localized basis function method. The numerical results show that the polarization properties are strongly dependent on structural parameters of the PCF. Furthermore, the proposed fiber was fabricated based on MMA monomer polymerization method in situ. So the proposed PCFs may be useful in the field of high birefringence polarization-maintaining optical communication.