Membranes with high conductivity, high selectivity, and high stability are urgently needed for high-power-density vanadium flow batteries (VFBs). Enhancing membrane conductivity presents many challenges, often resulting in sacrificing membrane selectivity and mechanical strength. To overcome this, new robust adamantane-based membranes with enhanced conductivity are constructed for VFB. Low-content basic piperazine (IEC = 0.78 mmol g⁻¹) and hydrophilic hydroxyl groups are introduced into highly rigid, hydrophobic adamantane containing poly(aryl ether ketone) backbone (PAPEK) and then selectively swelled to induce microphase separation and form ion transport pathways. The highly rigid and hydrophobic PAPEK exhibits high swelling resistance and provides the membranes with slight swelling, high selectivity, and high mechanical strength. The selective swelling temperature has a significant influence on the areal resistance of the resulting membrane, e.g., the PAPEK-130 membrane, when selectively swelled at 130 °C, has low areal resistance (0.22 Ω∙cm²), which is approximately two-fifths that of the PAEKK-60 membrane (treated at 60 °C, 0.57 Ω∙cm²). Consequently, the resulting PAPEK membranes exhibit low swelling, high selectivity, and low areal resistance, with the VFB constructed with a PAPEK-90 membrane exhibiting excellent energy efficiency (91.7%, at 80 mA∙cm⁻², and 80.0% at 240 mA∙cm⁻²) and stable cycling performance for 2000 cycles.