Ordered (-aadcbbcd-) polyamides were prepared by the direct polycondensation of a pair of symmetric monomers (XabX), bis(2,4,6-trichlorophenyl) isophthalate or bis(2,4,6-trichlorophenyl) adipate (XaaX) and 5-nitroisophthalic acid (XbbX),with a nonsymmetric monomer (YcdY), 4-aminobenzohydrazide, using the activating agent diphenyl (2,3-dihydro-2-thioxo-3-benzoxazolyl)phosphonate. The polycondensation was carried out by mixing the monomers all at once, yielding the ordered polyamide with inherent viscosities up to 0.30 dL/g. The authentic ordered and random polyamides were prepared to verify the structures of ordered polyamide. The microstructures of polyamides obtained were investigated by means of C-13 NMR spectroscopy, and it has been found that the polyamides obtained had the expected ordered structures. Furthermore, the model reactions were studied in detail to demonstrate the feasibility of ordered polyamidation.