The development of efficient electron donor (or hole-transporting) molecules that can be used in various optoelectronic device fields is highly demanded. In this work, a novel class of triptycene-based three-dimensional (3D) triphenylamine (TI-TPA) derivatives with different end substituents was designed and prepared for transparent electron donor materials. Owing to the rigid 3D triptycene framework, the obtained TI-TPA derivatives had an amorphous morphology with high thermal decomposition temperature. The oxidation potential of these TI-TPA derivatives decreased as the electron donating strength of the end substituent increased. Among TI-TPA derivatives, TI-TPA-OMe exhibited the highest HOMO level (-5.31 eV) which is similar to that of Spiro-OMeTAD (-5.22 eV). In addition, TI-TPA-OMe was found to form a strong charge transfer complex with the triptycene-based acceptor TI-BQ, leading to a new absorption band at around 640 nm. These results can be applied for developing efficient electron donor materials that can mimic the advantages of the spiro-linked structure and TPA units of Spiro-OMeTAD.