We report the effect of water nanoconfinement on the thermal transport properties of two neighbor hydrophilic quartz interfaces. A significant increase and a nonintuitive, nonmonotonic dependence of the overall interfacial thermal conductance between the quartz surfaces on the water layer thickness were found. By probing the interfacial structure and vibrational properties of the connected components, we demonstrated that the mechanism of the peak occurring at submonolayer water originates from the freezing of water molecules at extremely confined conditions and the excellent match of vibrational states between trapped water and hydrophilic headgroups on the two contact surfaces. Our results show that incorporation of polar molecules into hydrophilic interfaces is very promising to enhance the thermal transport through thermally smooth connection of these interfaces. © 2010 American Chemical Society.