The advancement in developing highly efficient hole transport materials for OLED devices has been a challenge over the past several years. For an efficient OLED device, there should be an efficient promotion of charge carriers from each electrode and effective confinement of triplet excitons in the emissive layer of the phosphorescent OLED (PhOLED). Thus, the development of stable and high triplet energy hole transport materials is in urgent demand for high-performing PhOLED devices. The present work demonstrates the development of two hetero-arylated pyridines as high triplet energy (2.74-2.92 eV) multifunctional hole transport materials to reduce the exciton quenching and to enhance the extent of charge carrier recombination in the emissive layer. In this regard, we report the design, synthesis, and theoretical modeling with electro-optical properties of two molecules, namely PrPzPy and MePzCzPy, with suitable HOMO/LUMO energy levels and high triplet energy, by incorporating phenothiazine as well as other donating units into a pyridine scaffold, and finally developing a hybrid phenothiazine-carbazole-pyridine based molecular architecture. The natural transition orbital (NTO) calculations were done to analyze the excited state sensation in these molecules. The long-range charge transfer characteristics between the higher singlet and triplet states were also analyzed. The reorganization energy of each molecule was calculated to examine their hole transportability. The theoretical calculations for PrPzPy and MePzCzPy revealed that these two molecular systems could be promising materials for the hole transport layer of OLED devices. As a proof of concept, a solution-processed hole-only device (HOD) of PrPzPy was fabricated. The increase in current density with an increase in operating voltage in the range of ∼3-10 V supported that the suitable HOMO energy of PrPzPy can facilitate the hole transportation from the hole injection layer (HIL) to the emissive layer (EML). These results indicated the promising hole transportability of the present molecular materials.