The paper describes the impact of the crystallographic orientation of an n-type GaAs substrate on the electrical properties of a sulfonated polyaniline (SPAN) thin film with a thickness of 120 nm grown on different n-type GaAs substrates orientation, which are (100), (311)A, and (311)B GaAs planes. Electrical characterization was performed by using current density-voltage (J−V) at room temperature and different temperatures (60−360 K). An ideality factor (n), a Schottky barrier height (Φb), and an activation energy (E a) were extracted from forward J−V characteristics. From the J−V results, it was obtained that the rectification value at 0.5 V for the SPAN/(311)B GaAs hybrid device is higher than those for SPAN grown on the (100) and (311)A GaAs planes. Furthermore, as the temperature of the three heterojunction devices rises, the value of Φ b increases, n drops, and E a rises. The E a measurements revealed that E a for the SPAN/(311)B n-type GaAs heterostructure is lower than those for SPAN samples grown on the (100) and (311)A n-type GaAs planes. This could be related to the low number of defects in SPAN/(311)B than the other two samples. These results make SPAN with a thickness of 120 nm grown on the high index GaAs planes an interesting hybrid device for future devices applications.