LAUSR

A new type of armored droplet, a so‐called polyhedral liquid marble, is introduced in this work. These armored liquid marbles consist of liquid droplets stabilized by hydrophobic hexagonal plates made of poly(ethylene terephthalate), which adsorb to the liquid–air interface. Depending on the specific combination of plate size and droplet diameter, the plates self‐assemble into highly ordered hexagonally arranged domains. Even tetrahedral‐, pentahedral‐, and cube‐shaped liquid marbles composed of only 4 to 6 plates are demonstrated. During evaporation of the internal liquid, due to the high adsorption energy of the plates at the liquid–air interface, the overall surface area stays constant, resulting in strongly deformed polyhedral liquid marbles. In line with this, highly asymmetric polyhedral liquid marbles and letters are obtained due to the strong interfacial jamming exerted by the rigid hexagonal plates. This is particularly pronounced for larger plate sizes, leading to liquid marbles with unusually sharp edges (for example, rectangular edges). The polyhedral liquid marbles exhibit various stimuli‐responsive behaviors simultaneously being exposed to water, ammonia, or tetrahydrofuran vapors. Air‐driven polyhedral liquid marbles floating on water can reach velocities of several centimeters per second.