Diamond is a promising material to develop sensors for applications in harsh environments. To increase the sensitivity of diamond temperature sensors the effect of thermionic hole emission (TE) over an energetic barrier formed in the interface between highly boron-doped p-type and intrinsic insulating diamond areas has been suggested. To study the TE of holes a p-i-p diode has been fabricated and analyzed by electrical measurements in the temperature range between 300 K and 700 K. The experimental results have been compared with numerical simulations of its electrical characteristics. Based on a model of the thermionic emission of carriers into an insulator it has been suggested that the temperature sensitivity of the pi-p diode on diamond is strongly affected by the re-emission of holes from a group of donor-like traps located at a level of 0.7-1.0 eV above the valence band. The mechanism of thermal activation of the current includes a spatial redistribution of the potential, which results in the TE regime from a decrease of the immobilized charge of the ionized traps within the i-zone of the diode and the correspondent lowering of the forward biased barrier. The characteristics of the p-i-p diode were studied with regard to temperature sensor applications. The temperature coefficient of resistance (TCR = - 0.05 K-1) for temperatures above 600 K is about four times larger than the maximal attainable TCR for conventional boron-doped diamond resistors.