Poly(2,6-dimethyl-phenyleneoxide)s (PPO)s with photo-crosslinkable azide groups were employed as macromolecular crosslinker for poly(vinylbenzyl chloride) (PVBC)-based anion exchange membranes (AEMs). The crosslinked AEMs were achieved by solution casting and UV-irradiation, subsequently quaternization with trimethylamine. Although the presence of azide groups in IR spectra in crosslinked AEMs suggested the incomplete reaction of azide groups using UV-irradiation, the gel fractions were more than 85% indicating the successful crosslinking between PVBC and PPO macromolecular crosslinker. The key properties of the crosslinked AEMs, such as mechanical property, ion exchange capacity, thermal stability, water uptake, ion conductivity, alkaline stability and initial H-2/O-2 fuel cell performance were investigated. Excellent mechanical properties were observed for all of the crosslinked AEMs. The as-obtained AEMs showed comparable lambda-normalized hydroxide conductivity with previous reported crosslinked AEMs. The highest hydroxide conductivity of 14.8 mS/cm at 20 degrees C was achieved for the crosslinked AEMs with IEC value of 1.95 meq./g in spite of its low water uptake (19.8 wt%). Moreover, excellent alkaline stability was observed for crosslinked AEMs, 15% decrease in hydroxide conductivity after alkaline stability testing 1 M NaOH at 80 degrees C for 500 h, while the conductivity of uncrosslinked membrane with similar IEC value decreased sharply with 58% of conductivity loss after only 120 h. The improved alkaline stability of the crosslinked AEMs may be derived from its compact crosslinked architecture, protecting the cations from severe degradation. A peak power density of 11 mW/cm(2) was obtained at 16 mA/cm(2) when the crosslinked AEM was used as polymer electrolyte membrane in H-2/O-2 alkaline fuel cell at 60 degrees C.