In order to obtain a flexible aerogel substrate for conductive materials used in the electrode, polydopamine-anchored cellulose nanofiber (PDA@CNF) was introduced into a polyethylene imine-poly(vinyl alcohol) (PEI-PVA) cross-linking network which used 4-formylphenylboronic acid (4FPBA) as bridge. The incorporation of rigid CNF as a structural scaffold effectively improved the pore architecture of the aerogel, potentially providing substantial advantages for the infiltration and deposition of conductive materials. Additionally, the outstanding stability and flexibility exhibited by the aerogel in aqueous solutions suggest its significant potential for applications in flexible electrodes. Furthermore, electrochemical experiments showed that the rapid pathway formed between PDA and PEI could enhance the charge-transfer rate within the aerogel substrate. It is anticipated that such an enhancement would significantly benefit the electrochemical attributes of the electrode. Inspired by mussels, our introduced PDA-anchored rigid CNF into flexible polymer networks to fabricate aerogel substrates for electrode materials. This study would contribute to the development and utilization of flexible electrodes while reducing carbon footprint in energy production and conversion processes.