Design and fabrication of alternative proton exchange membrane (PEM) with high proton conductivity is crucial to the commercial application of PEM fuel cell. Inspired by the bioadhesion principle, dopamine‐modified halloysite nanotubes (DHNTs) bearing –NH2 and –NH– groups are facilely synthesized by directly immersing natural halloysite nanotubes (HNTs) into dopamine aqueous solution under mild conditions. DHNTs are then embedded into sulfonated poly(ether ether ketone) (SPEEK) matrix to prepare hybrid membranes. HNTs‐filled hybrid membranes are prepared for comparison. The microstructure and physicochemical properties of the membranes are extensively investigated. Fourier transform infrared analysis implies that ordered acid–base pairs (e.g., –S–O–…+H–HN–, –S–O–…+H–N–) are formed at SPEEK–DHNT interface through strong electrostatic interaction. In such a way, continuous surface‐induced ion‐channels emerge along DHNTs. Although the incorporation of DHNTs reduces the channel size, water uptake, and area swelling of the hybrid membranes, which in turn would reduce the vehicle‐type proton transfer, the acid–base pairs create continuous pathways for fast proton transfer with low energy barrier via Grotthuss mechanism. Consequently, DHNT‐filled hybrid membrane with 15% DHNTs achieves a 30% increase in proton conductivity and a 52% increase in peak power density of single cell when compared with SPEEK control membrane, particularly.

As a key component of low‐cost anion exchange membrane fuel cells (AEMFCs), anion exchange membranes (AEMs) are far from commercial application, because of dissatisfactory alkaline stability and conductivity. Herein, a new insight is proposed to prepare high performance AEMs by constructing of confined ion channel. With an intermediate oligomer produced before the main copolymerization, novel poly(vinyl‐carbazolyl aryl piperidinium) AEMs with confined sub‐2‐nm ion channel are successfully prepared. The unique sub‐2‐nm ion channel enable membranes ultrahigh hydroxide conductivity of 261.6 mS cm−1, and the state‐of‐the‐art chemical stability over 5000 h. Moreover, the AEMs also exhibit good mechanical stability with lower water uptake and dimensional swelling. Based on the as‐prepared AEMs and ionomer, fuel cells exhibit outstanding peak power density of 1.8 and 0.2 W cm−2 with Pt‐based catalysts and completely non‐precious metal catalysts, respectively.