A series of fluorescent donor- acceptor (D-A) alternating copolyimides (P1, P2, P3 and P4) with 4-quinolin-8-yloxy linked triphenylamine main polymer chain have been synthesized by conventional polycondensation. All the synthesized co-polyimides were characterized by elemental, gel permeation chromatography and FTIR spectral analysis. These newly prepared PIs possess HOMO energy levels in range of - 4.74 to - 4.78 eV and have medium optical band gaps. The photoluminescence spectral analysis revealed blue to violet emission with appreciable efficiency with lower onset oxidation potentials suitable for the facile hole injection materials. All the photophysical and electrochemical properties were also explored in context of effect of the pendant 4- quinolin-8-yloxy, indicating suitable combination of donor (TPA) on one hand and imide and pendant as acceptor on both ends.