The unique characteristic of carbon dots (C-dots), such as optical and electrical properties, have been integrated into polyvinyl alcohol (PVA) to realize composites with synergistic. In this work, C-dots have been synthesized from inner cassava peels using simple methods at low temperatures. The C-dots were added to PVA, which is influenced the characteristic based on spectroscopy. The complex formation between PVA and C-dots was investigated by FTIR spectroscopy. The C-dots contributed to UV-Vis spectroscopy characteristic of PVA/C-dots with the absence of a new peak of absorbance spectra. Besides, C-dots also supported the electrochemical impedance spectroscopy characteristic of PVA/C-dots, so the highest ionic conductivity is induced by the enhancement of amorphous PVA when the c-dots content is increased.