Methods for effective synthesis for the four possible isomeric 3,9-diphenylullazine carboxaldehydes and reactive halogen intermediates are described. Ullazine donor-acceptor (D-A) dyes were studied using UV/Vis, photoluminescence (PL) spectroscopy and cyclic voltammetry. X-ray single crystal diffraction analysis independently confirmed the structures of two key intermediates. A D-A dye based on ullazine with dihexylmalonate acceptor was tested as a dopant-free hole-transporting material (HTM) in a perovskite solar cell, exhibiting promising power conversion efficiency (PCE) reaching 13.07 %.