We have revealed the kinetic advantage of the aza-Wittig polymerization over the conventional diamines/dialdehydes polycondensation system for the effective preparation of end-functionalized, pi-conjugated poly(azomethine)s. The synthesized polymers P1 and P2 possess hexyl groups and POSS units at the chain ends, respectively. Both polymers were highly soluble in common organic solvents including CHCl3, CH2Cl2, THF, benzene, and toluene at room temperature. The thermal stability of POSS-modified poly(azomethine) P2 (temperature of 10% weight loss; T-10 = 381 degrees C) was high as compared to that of poly(azomethine) without POSS units P1 (T-10 = 372 degrees C) because of the siliceous bulky POSS segments at the chain ends. Further, UV-vis absorption Study in dilute CHCl3 Solution (1.0 x 10(-5) M) demonstrated that both polymers had the same absorption maxima at 454 nm, resulting from the extension of the pi-electron delocalization length of both polymers via the pi-conjugated poly(azomethine) backbone. In the film state, UV-vis absorption spectra. fluorescence quantum yields (Phi(F)), XRD patterns, and TEM images supported that bulky three-dimensional POSS groups it( the chain ends effectively suppress intermolecular aggregations of the individual poly(azomethine).