Organo-soluble, shape-persistent oligo- and poly(p-benzamide)s were synthesized and characterized. A triethylene glycol (TEG) substituent was introduced to the p-aminobenzoic acid monomer structure as a solubilizing side chain giving 4-amino-2-triethylene glycol benzoic acid. This new monomer was polymerized by the facile polycondensation of the corresponding acid halide derivative of the amine hydrochloric salt. Additionally, a well-defined heptamer was prepared from this monomer on a peptide synthesizer as a model compound. The TEG-substituted oligomers and polymers exhibited good solubility yet high aggregation tendency in common polar and nonpolar organic solvents. The solution self-organization of the poly(2-TEG-p-benzamide) was examined by GPC, NMR, and UV/vis spectroscopy. Transmission electron microscopy (TEM) allowed the visualization of the supramolecular assemblies, showing the formation of micrometer-sized rigid superstructures.