Micro-supercapacitors are a kind of state-of-the-art energy storage devices and have great potential to be developed in portable and wearable electronics. Here, we report a novel strategy for scalable fabrication of all printed solid-state micro-supercapacitors with multilayer structure via multi-material 3D printing technique. To obtain electrode materials, we synthesize polypyrrole/polyaniline coaxis nanotubes by utilizing the self-degraded template polymerization method and in situ electrochemical polymerization. The as-prepared aqueous composite electrode ink shows significant shear thinning behavior and excellent processability: a complex electrode patterning with 484 retractions was proved. In addition, the inks are well-adapted to various substrates (paper, texitle, plastic film etc), allowing the device to be printed onto different substrates, even directly on the desired surface. As a conceptual exhibition, we design two schemes of in situ fabricated energy storage devices to meet the ever-changing energy needs and expand the application range of micro-supercapacitors. The transferable tape-type micro-supercapacitors can be stuck to any surfaces where energy is needed immediately. The in situ fabricated wearable micro-supercapacitor on lab-gown shows promising performance and excellent flexibility.