Dual electrochromic and electrofluorochromic materials have gained much attention for various intelligent applications, such as sensors, displays, and wearable devices. We report here the synthesis of two hydrolysable crosslinked siloxane monomers via nucleophilic reaction, followed by drop-casted onto the hydrophilic indium-tin oxide substrate. After hydrolysis during cyclic voltammetry, the aforementioned two functional siloxane monomers are transformed into a network polymer film. The resulting polymer film exhibits good electrochromic performance with outstanding stability, due to its inherent robust crosslinking structure and strong adhesion to the ITO substrate. Moreover, a fascinating electrofluorochromic behavior has also been disclosed, due to the interplay between electroactive oligoaniline and fluorescent fluorene groups.