We have used electrically detected magnetic resonance (EDMR) to study a series of multilayer organic devices based on aluminum (III) 8-hydroxyquinoline (Alq₃). These devices were designed to identify the microscopic origin of different spin-dependent processes, i.e. hopping and exciton formation. The EDMR signal in organic light-emitting diodes (OLEDs) based on Alq₃ is only observed when the device is electroluminescent and is assigned to spin-dependent exciton formation. It can be decomposed in at least two Gaussians: one with peak-to-peak line (ΔH_PP) of 1.6 mT and another withΔH_PP of 2.0 to 3.4 mT, depending on bias and temperature. The g-factors of the two components are barely distinguishable and close to 2.003. The broad line is attributed to the resonance in Alq3 anions, while the other line is attributed to cationic states. These attributions are supported by line shape and its electrical-field dependence of unipolar Alq₃-based diodes, where hopping process related to dication and dianion formation is observed. In these unipolar devices, it is shown that the signal coming from spin-dependent hopping occurs close to organic semiconductor/metal interfaces. The sign of the magnetic-resonance-induced conductivity change is dominated by charge injection rather than charge mobility. Our results indicate that the probability of singlet exciton formation in our OLEDs is smaller than 25%.