Rare earth elements (REEs) play a crucial role in modern technology owing to their unique physical and chemical properties. However, their distribution and content in the environment have been continuously altered by human activities and industrial development. On-site, sensitive, and fast analysis of multiple REEs is essential, but remains a challenging task. This study introduces a flexible superhydrophobic film (FSF) combined with laser-induced breakdown spectroscopy (LIBS) for the high-sensitivity and rapid detection of multiple REEs in aqueous solutions. By employing a flexible substrate film with micron-sized pockets as a protective layer for fragile hydrophobic nanostructures, the FSF exhibits enhanced hydrophobicity and unique self-cleaning properties. These features render it more convenient and flexible in both preparation and application. Furthermore, microwave-assisted droplet evaporation is achieved on hydrophilic dot arrays of the FSF, thereby enabling efficient element-targeted enrichment. This is seamlessly integrated with the instantaneous and high-throughput analysis provided by LIBS. The proposed method demonstrates the ability to detect six REEs in aqueous solutions simultaneously with high sensitivity and high speed within 25 min. The limits of detection of REEs are obtained at the μg/L level, which is several orders of magnitude lower than previously reported LIBS techniques. The FSF-LIBS approach offers a potential tool for on-site elemental analysis, energy utilization, geochemical cycles monitoring, and environmental monitoring.