A carboxyl-terminated benzimidazole trimer was synthesized as a crosslinker by controlling the ratio of 3,3′-diaminobenzidine and isophthalic acid. Composite membranes were obtained by mixing the benzimidazole trimer and sulfonated poly(ether ether ketone) (SPEEK) together. Cross-linked membranes were obtained by heating the composite membranes at 160 °C. All of the properties of the cross-linked membranes were significantly increased, including proton conductivity, methanol permeability and water uptake due to the more compact structure compared to the non-cross-linked membranes. The cross-linked SPEEK-BI7 and cross-linked SPEEK-BI11 had excellent proton conductivities (0.22 and 0.19 S cm⁻¹) at 80 °C, which were higher than that of Nafion 117 (0.125 S cm⁻¹). Transmission electron microscopy (TEM) analysis revealed a clear microphase separated structure of cross-linked membranes. Other properties, such as thermal and mechanical stability, required for use as a proton exchange membrane (PEM) have been investigated. The cross-linked membranes showed improved properties over membranes without crosslinking.