In this study, the resistive switching phenomena in TiN/Ti/HfO2/Ti metal–insulator–metal stacks is investigated, mainly focusing on the analysis of set and reset transitions. The electrical measurements in a wide temperature range reveal that the switching transitions require less voltage (and thus, less energy) as temperature rises, with the reset process being much more temperature sensitive. The main conduction mechanism in both resistance states is Space-charge-limited Conduction, but the high conductivity state also shows Schottky emission, explaining its temperature dependence. Moreover, the temporal evolution of these transitions reveals clear differences between them, as their current transient response is completely different. While the set is sudden, the reset process development is clearly non-linear, closely resembling a sigmoid function. This asymmetry between switching processes is of extreme importance in the manipulation and control of the multi-level characteristics and has clear implications in the possible applications of resistive switching devices in neuromorphic computing.