We produced kilometer-long, endlessly parallel, spontaneously piezoelectric and thermally stable poly(vinylidene fluoride) (PVDF) micro- and nanoribbons using iterative size reduction technique based on thermal fiber drawing. Because of high stress and temperature used in thermal drawing process, we obtained spontaneously polar γ phase PVDF micro- and nanoribbons without electrical poling process. On the basis of X-ray diffraction (XRD) analysis, we observed that PVDF micro- and nanoribbons are thermally stable and conserve the polar γ phase even after being exposed to heat treatment above the melting point of PVDF. Phase transition mechanism is investigated and explained using ab initio calculations. We measured an average effective piezoelectric constant as -58.5 pm/V from a single PVDF nanoribbon using a piezo evaluation system along with an atomic force microscope. PVDF nanoribbons are promising structures for constructing devices such as highly efficient energy generators, large area pressure sensors, artificial muscle and skin, due to the unique geometry and extended lengths, high polar phase content, high thermal stability and high piezoelectric coefficient. We demonstrated two proof of principle devices for energy harvesting and sensing applications with a 60 V open circuit peak voltage and 10 μA peak short-circuit current output.