We achieved a multiscale description of the thermal conductivity of cellulose nanocrystals (CNCs) from single CNCs (similar to 0.725.7 W m(1) K-1) to their organized nanostructured films (similar to 0.220.53 W m(1) K-1) using experimental evidence and molecular dynamics (MD) simulation. The ratio of the approximate phonon mean free path (similar to 1.75.3 nm) to the lateral dimension of a single CNC (similar to 520 nm) suggested a contribution of crystalcrystal interfaces to polydisperse CNC films heat transport. Based on this, we modeled the thermal conductivity of CNC films using MD-predicted single crystal and interface properties along with the degree of CNC alignment in the bulk films using Hermans order parameter. Film thermal conductivities were strongly correlated to the degree of CNC alignment and the direction of heat flow relative to the CNC chain axis. The low interfacial barrier to heat transport found for CNCs (similar to 9.4 to 12.6 m2 K GW(1)), and their versatile alignment capabilities offer unique opportunities in thermal conductivity control.