Two different approaches to synthesize flexible, redox-active, and electrochromic hybrid copolymers poly(3,4-ethylenedioxythiophene)-co-polydimethylsiloxanes (PEDOT-co-PDMSs) are proposed. PEDOT-co-PDMSs were obtained via chemical oxidative polymerization and electrochemical polymerization of thienyl-terminated polydimethylsiloxanes and 3,4-ethylenedioxythiophene. The detailed structural and elemental characterization of the obtained PEDOT-co-PDMSs was provided by a combination of methods including nuclear magnetic resonance, Fourier-transform infrared, ultraviolet–visible, and X-ray photoelectron spectroscopies. The electrochemical behavior of PEDOT-co-PDMS films was studied by electrochemical impedance spectroscopy and cyclic voltammetry. The flexible hybrids demonstrate not only enhanced capacitive behavior compared to pure PEDOT (capacitive contribution achieves 89%) but also effective electrochromic performance with coloring efficiency reaching ηC= 180 cm2·C–1. The synthesized hybrid PEDOT-co-PDMSs are promising materials for flexible electronics, electrochromics, energy storage devices, and so on.