A series of ordered polymers can be prepared by direct polycondensation of nonsymmetric monomers using diphenyl(2,3-dihydro-2-oxo-3-benzothiazolyl)phosphonate (1) as a condensing agent. The methodology and requirements for the preparation of ordered polymer are first presented. Then, the following ordered polymer syntheses are described: (1) ordered polyamides (head-to-head or tail-to-tail) from a symmetric monomer and a nonsymmetric monomer. (2) the ordered polyamide (head-to-tail) from a symmetric monomer and a nonsymmetric monomer. (3) the ordered (-abcd-) polymer from a pair of two symmetric monomers and a nonsymmetric monomer. (4) the ordered (-abcdef-) polymer from nonsymmetric monomers, XabX, YcdY, and ZefZ.