Advanced methods, allowing the controllable synthesis of ordered structural nanomaterials with favorable charges transfer and storage, are highly important to achieve ideal supercapacitors with high energy density. Here, we report a microliter droplet-based method to stably synthesize hierarchical-structured metal-organic frameworks/graphene/carbon nanotubes hybrids. Due to the confined ultra-small-volume reaction, the well-defined hybrids possess large specific-surface-area (1206 m 2 g -1 ), abundant ionic-channels (narrow pore of 0.86 nm) and nitrogen active-sites (10.63%), creating 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. Based on those outstanding features, a self-powered system that directly converts and stores solar-energy into electric-energy is designed to power displays, which will guide the progress of new electrodes architecture and energy-storage industry.