Interdependent decisionmaking of individuals in social systems can be modelled by games played on complex networks. Players in such systems have bounded rationality, which influences the computation of equilibrium solutions. It has been shown that the ‘system rationality’, which indicates the overall rationality of a network of players, may play a key role in the emergence of scale-free or core-periphery topologies in real-world networks. In this work, we identify optimal topologies and mixing patterns of players which can maximise system rationality. Based on simulation results, we show that irrespective of the placement of nodes with higher rationality, it is the disassortative mixing of node rationality that helps to maximize system rationality in a population. In other words, the findings of this work indicate that the overall rationality of a population may improve when more players with non-similar individual rationality levels interact with each other. We identify particular topologies such as the core-periphery topology, which facilitates the optimisation of system rationality. The findings presented in this work may have useful interpretations and applications in socio-economic systems for maximizing the utility of interactions in a population of strategic players.