Field-assisted thermionic emission within a sputter-deposited, nanocrystalline thin film of CuAlO2.06 is observed for the first time, and explained in terms of the Poole-Frenkel model. The presence of adsorbed oxygen ions as trap-states at the grain boundary regions of the nanostructured thin film is considered to manifest this phenomenon. Under an applied field, the barrier of the trap potential is lowered and thermal emission of charge carriers takes place at different sample temperatures to induce nonlinearity in the current (I)-voltage (V) characteristics of the nanomaterial. Fitting of the Poole-Frenkel model with the I-V data shows that the nonlinearity is effective above 50 V under the operating conditions. Calculations of the energy of the trap level, acceptor level and Fermi level reveal the existence of deep level trap-states and a shallow acceptor level with acceptor concentration considerably higher than the trap-states. Hall measurements confirm the p-type semiconductivity of the film, with a hole concentration around 10(18) cm(-3). Thermopower measurements give a room-temperature Seebeck coefficient around 130 μV K(-1). This temperature-dependent conductivity enhancement within CuAlO2 nanomaterial may find interesting applications in transparent electronics and high-voltage applications for power supply networks.