Abstract Here we applied solar energy converted into biomass to produce efficient biodegradable flexible hydrophobic thermoelectric (TE) material with nanocellulose (NC) film as environmentally friendly functional substrate. We used fast-growing perennial herb Miscanthus × giganteus to manufacture flexible 12 µm thick NC film with stable monoclinic cellulose structure (Iβ), high crystallinity index (CI = 78%) and average crystallite size 3 – 4 nm. Through the low-temperature cheap and scalable method Successive Ionic Layer Adsorption and Reaction (SILAR) we deposited copper iodide (CuI) films on NC substrates and thus obtained non-toxic TE materials CuI/NC, which can be water-repellent, as their contact angles reach 140°. In the most efficient TE sample CuI/NC, the obtained via SILAR 0.39 µm thick nanostructured CuI film consists of cubic (1 1 1)-oriented γ-CuI crystals with faceted surfaces of ~200–300 nm. The high electrical conductivity (σ) and shape of the σ vs. temperature (T) curve of this CuI/NC sample is realized through suppression of grain boundary scattering due to tunneling currents in CuI. The CuI/NC material has large thermoelectric power factor (PF) that grows with increasing temperature and reaches value 140 μW·m−1·K−2 at T = 333 K. This PF is the record for biodegradable flexible thermoelectric materials. At ΔT = 40 K the CuI/NC-based single p-CuI thermoelectric leg generates open circuit voltage 3.5 mV, short circuit current 4 µA, and power 3.8 nW, and these output parameters can be further improved through a thickening the CuI film in CuI/NC by increasing the number of SILAR cycles.