A new generation of fast breeder reactors (FBRs) is under development with the objective of making nuclear energy more sustainable. Most promising reactor designs are loaded, at least during their early phase of deployment, with UO2–PuO2 mixed oxide fuel (MOX). Concentrations of plutonium dioxide that are foreseen for FBRs range up to 30 mol%. This highlights the need for a sound and deep knowledge of the thermophysical properties of PuO2. This statement is valid in the case of heat capacity, as evaluations on MOX fuel are usually carried out by using the Neumann–Kopp rule. Heat capacity is relevant for thermal conductivity and performance under transient conditions. However, measurements on the heat capacity of plutonium dioxide are scarce or even lacking at high temperature. Numerical methodologies such as molecular dynamics (MD) calculations have been employed to overcome the difficulties encountered in experimental measurements. Besides numerical also theoretical models have been applied as valuable tools for interpretation of enthalpy measurements. Nevertheless, due to the mentioned lack of experimental measurement issues such as the existence of the Bredig transition and the formation of defects at high temperatures are still debated in nuclear fuel research. Excess enthalpy seen in measurements of actinides oxides has been explained by means of either electronic disorder or anion disorder. In the case of plutonium dioxide, a common consensus has been reached on the hypothesis that anion disorder leads to a significant increase in heat capacity at high temperature. Konings and Beneš have developed a model that accounts for this phenomenon. Their correlation has been often included in models of heat capacity and employed for recommendations. However, in the high-temperature region, MD calculations showed an underestimation of model predictions that was not compensated by the presence of a peak of heat capacity that has been interpreted as the Bredig transition. Based on these observations, this paper presents MD evaluations on the heat capacity of PuO2 at high temperature that are mostly focused on the formation energy of oxygen Frenkel pairs (OFPs) and its correlation with the model proposed by Konings and Beneš. Besides an interatomic potential published in the open literature and developed in compliance with the experimental thermal expansion of PuO2, a second interatomic potential has been applied in calculations. This latter is featured by a lower formation energy of OFP. The contribution due to defects formation was calculated by means of a simplified theoretical model of heat capacity. Results of calculations in the very high-temperature domain showed an increase in the contribution due to OFP defects consistent with the model by Konings and Beneš. Predictions suggest the onset of a premelting transition around 85% of melting temperature without the presence of a peak of heat capacity. Major deviations from the recommended model have been noted in the intermediate temperature region where the effect of clustering of defects should play a significant role. Therefore, the value of formation energy of OFP proposed by Konings and Beneš could be interpreted as an effective value that accounts for the two processes (defects clustering and premelting transition) that could contribute, according to our results, to the heat capacity of plutonium dioxide at high temperature. This conclusion is consistent with the numerical evaluations of OFP formation energy that are in general higher than proposed by Konings and Beneš.