The liquid structuring at the interface governs the mechanism of interfacial heat transport in nanoscale systems. Despite the availability of synthetic organic fluids, water is still considered one of the best liquids for convective heat transfer. However, in confined nanochannels, the laws of classical physics breaks down and mechanism of heat transport is governed by Kapitza resistance and interfacial liquid structuring. Hence, the efficacy of different materials needs to be further investigated to tailor efficient thermal management systems. We used classical molecular dynamics simulations to investigate the effects of liquid structuring at different temperatures on the heat transfer across graphene-water and graphene-perfluorohexane interfaces. The results shows that long-chain molecules, like perfluorohexane, can retain the layering even at a higher temperature than water. On the other hand, water increases its mobility at higher temperatures, and the liquid layer density depletes rapidly.