Summary: Direct methanol fuel cell (DMFC) is considered as one of the next‐generation power sources for portable electronic devices. However, the problems of structure and materials of the membrane electrode assembly (MEA) must be resolved if it is applied in flexible electronic devices. The traditional materials of MEA used in DMFC cannot bend and are easy to break. Moreover, the existence of a microporous layer increases the likelihood of separation of the gas diffusion layer (GDL) and catalytic layer. Herein, we develop a simple electrospinning method to prepare flexible titanium carbide/carbon nanofibers (TiC/CNFs) film used as GDL. TiC/CNFs film plays a GDL and a microporous layer dual role. The MEA exhibits enhancing performance and excellent flexibility. The maximum power density of flexible DMFC can reach 20.2 mW/cm2, compared with the GDL made of traditional carbon cloth (18.1 mW/cm2), the maximum power density rises by 11.6%. After 50 consecutive bends, the voltage drops less than 10%. This work would promote the flexibility of DMFC. [ABSTRACT FROM AUTHOR]