In this research a new structurally-modified monomer, 2,2′-bis[(p-phenoxy phenyl)]-4,4′-diaminodiphenyl ether (PPAPE) was synthesized by a three-step manner starting from 4,4′-dinitrodiphenyl ether. Novel classes of wholly aromatic polyamides and polyimides were prepared from PPAPE through the conventional polycondensation reactions including triphenyl phosphate-activated phosphorylation method for the preparation of the polyamides and cyclodehydration of in situ-formed polyamic acid precursors for the preparation of the polyimides. n and w values were determined by GPC measurements. Crystallinity, organosolubility, and qualitative film characteristics of the resulting aromatic polyamides and polyimides were investigated. A low crystallinity extent was only observed using their wide-angle X-ray diffractograms. All polymers had excellent organosolubility in common polar solvents such as DMAc, DMF, DMSO, and NMP. The resulting well-designed polymers could also be cast into transparent and flexible films.