Abstract In this work, we used solar energy converted via photosynthesis into chemical energy of the biomass of the fast-growing perennial herb Miscanthus × giganteus for the manufacture of nanocellulose (NC) films, which are biodegradable alternative to common petroleum-based polymer substrates used in flexible electronics. To create the NC substrates, we applied an environmentally friendly method of organosolv delignification of plant raw materials carried out at a low temperature and in a relatively short time. Then by means of the low-temperature cheap and scalable method Successive Ionic Layer Adsorption and Reaction (SILAR) we deposited copper iodide (CuI) film of 0.72 µm thickness on both sides of the 12 µm thick NC substrate, and thus obtained light-weight and flexible biodegradable nontoxic thermoelectric material CuI/NC. Crystal structure, morphology, chemical composition, and optical, electrical and thermoelectric properties of the CuI/NC have been researched. Studies have shown that nanostructured p-type semiconductor CuI film in the CuI/NC TE material is quite dense and completely covers the NC surface. It has typical optical direct band gap ≈ 3.0 eV, is single-phase γ-CuI with crystallite sizes in the 19–25 nm range, with moderate dislocation density of (1.6–2.8) × 1015 lines/m2, and tolerable microstrains e of (4–9) × 10−3 a.u. The determined value of the Seebeck coefficient S is ~228 μV K−1, at that, S is constant in the temperature range 290–335 K. Together with the thermoelectric power factor ≈ 36 μW·m−1·K−2it is favorable for the use of CuI/NC as new thermoelectric material for an in-plane design of biodegradable flexible thin film thermoelectric generator (TEG). At temperature gradient of 50 K, the single p-CuI thermoelectric leg made from CuI/NC strip of 3 cm long and 0.5 cm wide generates open circuit voltage 8.4 mV, short circuit current 0.7 µA and maximum output power 1.5 nW. It corresponds to the output power density 10 µW/m2, and thus confirms the suitability of CuI/NC to obtain electricity by the harvesting the waste environmental heat.