Two poly(2-vinylpyridine)s fully quaternized with a ω-(4′-methoxy-4-biphenylyloxy)-alkyl group (alkyl chain of 9 and 11 carbon atoms) have been synthesized by the well known spontaneous polymerization of vinylpyridinium salts. When heated, these polymers (P2VPC9 and P2VPC11) show thermotropic liquid crystal properties. According to the X-ray diffraction data, the observed smectic mesophase in both polymers is of the type A (SA). Results are discussed in comparison with other molecular and polymeric pyridinium salts previously described. A molecular arrangement model for the P2VP derivatives is proposed.