Ultrasensitive detection of metallic elements in liquids has attracted considerable attention in fields such as environmental pollution monitoring and drinking water quality control. Hence, it is of great significance to develop a sensitive and simultaneous detection strategy for multiple metal elements in liquid. Laser-induced breakdown spectroscopy (LIBS) technology shows unique advantages because of its simple, rapid, and real-time in situ detection, but the laser energy will be greatly attenuated in the liquids; thus, the sensitivity of LIBS for direct detection of metal elements in liquid samples will decrease sharply. In this study, inspired by the structure of Stenocara beetle's back, a superhydrophobic biomimetic interface with hydrophilic array was prepared for enriching low-concentration targets into detection regions, and the biomimetic array LIBS (BA-LIBS) was successfully established. The ultrasensitive and simultaneous detection of nine metal elements in drinking water was realized based on the effective enrichment method. The limits of detection of the nine metal elements in mixed solution ranged from 8.3 ppt to 13.49 ppb. With these excellent properties, this facile and ultrasensitive BA-LIBS strategy might provide a new idea for the prevention and control of metal hazards in the liquid environment.