Inspired by the liquid uni-directional transportation on the peristome surface of Nepenthes, we fabricated a peristome-mimicking surface through high-resolution stereo-lithography and demonstrated the detailed uni-directional transportation mechanism from a micro-scaled view visualized through X-ray microscopy. Significantly, an overflow-controlled liquid uni-directional transportation mechanism is proposed and demonstrated. Unlike the canonical predictions for completely wetting liquids spreading symmetrically on a high-energy surface, liquids with varied surface tensions and viscosities can spontaneously propagate in a single preferred direction and pin in all others. In addition, we use this kind of 3D printed materials to separate micro-scaled water-in-oil droplets into pure phases, which is quite important in environmental protection, bioassays, and saving functional inks. So far, bulk oil–water separation has been achieved by membrane separation and sponge absorption. As a big advantage, we report that instead of the “plug-and-go” separation model, tiny water-in-oil droplets can be separated into pure water and oil droplets through “go-in-opposite ways” on curved peristome-mimetic surfaces, in milliseconds, without energy input. More importantly, this overflow controlled method can be applied to handle oil-in-oil droplets and viscous liquids with viscosities as high as hundreds centipoises, which markedly increases the range of applicable liquids for micro-scaled separation. Furthermore, the curved peristome-mimetic surface guides the separated drops in different directions with high efficiency. The fundamental understanding gained from this robust system enabled us to tailor advanced micro-computerized tomography scanning and stereo-lithography fabrication to mimic natural creatures and construct a wide variety of fluidic machines out of traditional materials.