In this paper, we present an extensive study of the electrical properties of organic-inorganic hybrid heterojunctions. Polyaniline (PANI) thin films were deposited by a very simple technique on (1 0 0) and (3 1 1)B n-type Gallium Arsenide (GaAs) substrates to fabricate hybrid devices with excellent electrical properties. The hybrid devices were electrically characterized using current-voltage (I-V), capacitance-voltage (C-V) and deep level transient spectroscopy (DLTS) measurements in the temperature range 20-440 K. The analysis of I-V characteristics based on the thermionic emission mechanism has shown a decrease of the barrier height and an increase of the ideality factor at lower temperatures for both hybrid devices. The interface states were analyzed by series resistance obtained using the C-G-V methods. The interface state density (D) of PANI/(1 0 0) GaAs devices is approximately one order of magnitude higher than that of PANI/(3 1 1)B GaAs devices. This behaviour is attributed to the effect of crystallographic orientation of the substrates, and was confirmed by DLTS results as well. Additionally, the devices show excellent air stability, with rectification ratio values almost unaltered after two years of storage under ambient conditions, making the polyaniline an interesting conductor polymer for future devices applications. (C) 2015 Elsevier B.V. All rights reserved.