Advanced methods, allowing the controllable synthesis of ordered structural nanomaterials with favourable charges transfer and storage, are highly important to achieve ideal supercapacitors with high energy density. Herein, we report a microliter droplet-based method to synthesize hierarchical-structured metal-organic framework/graphene/carbon nanotubes hybrids. The confined ultra-small-volume reaction, give well-defined hybrids with a large specific-surface-area (1206 m2 g-1 ), abundant ionic-channels (narrow pore of 0.86 nm), and nitrogen active-sites (10.63 %), resulting in high pore-size utilization (97.9 %) and redox-activity (32.3 %). We also propose a scalable microfluidic-blow-spinning method to consecutively generate nanofibre-based flexible supercapacitor electrodes with striking flexibility and mechanical strength. The supercapacitors display large volumetric energy density (147.5 mWh cm-3 ), high specific capacitance (472 F cm-3 ) and stably deformable energy-supply.