Carborane-based host materials were prepared to fabricate deep blue phosphorescence organic light-emitting diodes (PHOLEDs), which constituted three distinctive geometrical structures stemming from the corresponding three different isomeric forms of carboranes, namely, ortho-, meta-, and para-carboranes. These materials consist of two carbazolyl phenyl (CzPh) groups as photoactive units on each side of the carborane carbons to be bis[4-(N-carbazolyl)phenyl]carboranes, o-Cb, m-Cb, and p-Cb. To elaborate on the role of the carboranes, comparative analogous benzene series (o-Bz, m-Bz, and p-Bz) were prepared, and their photophysical properties were compared to show that advantageous photophysical properties were originated from the carborane structures: high triplet energy. Unlike m-Bz and p-Bz, carborane-based m-Cb and p-Cb showed an unconjugated nature between two CzPh units, which is essential for the blue phosphorescent materials. Also, the carborane hosts showed high glass transition temperatures (T(g)) of 132 and 164 °C for m-Cb and p-Cb, respectively. Albeit p-Cb exhibited slightly lower hole mobility when compared to p-Bz, it still lies at the high end hole mobility with a value of 1.1 × 10(-3) cm(2)/(V s) at an electric field of 5 × 10(5) V/cm. Density functional theory (DFT) calculations revealed that triplet wave functions were effectively confined and mostly located at either side of the carbazolyl units for m-Cb and p-Cb. Low-temperature PL spectra indeed provided unequivocal data with higher triplet energy (T(1)) of 3.1 eV for both m-Cb and p-Cb. p-Cb was successfully used as a host in deep blue PHOLEDs to provide a high external quantum efficiency of 15.3% and commission internationale de l'elcairage (CIE) coordinates of (0.15, 0.24).