We designed and synthesized phenanthro[9,10-d]imidazoles (PIs) in a D–A fashion to achieve a balance of charge carriers. Solution processable bottom gate–top contact organic field-effect transistors (OFET) were fabricated using a binary solvent system. The devices exhibited excellent p-channel characteristics with a high mobility of 0.70 cm² V^–1 s^–1 and an on/off ratio of 10⁷. Frontier molecular orbital levels and packing modes obtained from computational analysis supported the observed high mobility of the synthesized PI. Solvatochromism study of the compounds marked them insensitive toward solvent polarity. Photophysical behavior of the compounds in tetrahydrofuran/H₂O inferred efficient aggregate behavior. Scanning electron microscopy images of the aggregates in high water content show the formation of nanoaggregates. Dynamic light scattering experiments suggested a unimodal distribution of the nanoaggregates. This research work reports functionalized PIs with excellent OFET performance.