Conducting polymers are considered as an attractive option for energy storage system. In this paper, a unique quadruple thiophene-based polythiophene derivative (pPHBT) film was prepared through the electrochemical deposition from a star-shaped tri(bithiophene) benzene (PHBT). The electrodeposited pPHBT film may possess the microporous structure owing to the effective polymerization of star-shaped PHBT monomer. Also, the electrochemical, UV-vis and theoretical characterization of pPHBT film show that the oxidation reaction for this film should occur on the quadruple thiophene units. The unique structure of pPHBT may enable it with interesting electrochromic and energy storage properties. The pPHBT film shows the multicolor electrochromic character from yellow to green, and finally to blue color. The charging/discharging curves show that pPHBT film exhibits a high capacity of 96.7 mAh g(-1), which is viewed as a high value among the reported p-doped conducting polymer energy storage materials. Besides, the pPHBT film shows more symmetrical charging-discharging curves and relatively better cycling stability than the linear-structure poly(bithiophene) film. The combination of these fascinating properties results in an intelligent energy storage device changes its color based on its charged state so that the state of charge can be monitored by simple visual inspection. (C) 2019 Elsevier Ltd. All rights reserved.