The search for wearable electronics has been attracted great efforts, and there is an ever-growing demand for all-solid-state flexible energy storage devices. However, it is a challenge to obtain both positive and negative electrodes with excellent mechanical strength and match positive and negative charges to achieve high energy densities and operate voltages to satisfy practical application requirements. Here, flexible MXene (Ti₃C₂T_x)/cellulose nanofiber (CNF) composite film negative electrodes (MCNF) were fabricated with a vacuum filtration method, as well as positive electrodes (CP) by combining polyaniline (PANI) with carbon cloth (CC) using an in-situ polymerization method. Both positive and negative free-standing electrodes exhibited excellent electrochemical behavior and bendable/foldable flexibility. As a result, the all-pseudocapacitance asymmetric device of MCNF//CP assembled with charge-matched between anode and cathode achieves an extended voltage window of 1.5 V, high energy density of 30.6 Wh·kg⁻¹ (1211 W·kg⁻¹), and 86% capacitance retention after 5000 cycles, and the device maintains excellent bendability, simultaneously. This work will pave the way for the development of all-pseudocapacitive asymmetric supercapacitors (ASC) with simultaneously preeminent mechanical properties, high energy density, and wide operating voltage window.