In the framework of the Helmholtz ARCHES project, a multitude of robots, including rovers and drones, were prepared for the autonomous exploration of a test site at the foothills of Mt. Etna, Sicily—a terrain resembling extraterrestrial locations such as the Moon. To expand the suite of tools and sensors available for the exploration and investigation of the test site, we developed a laser-induced breakdown spectroscopy (LIBS) instrument for the geochemical analysis of local geological samples. In alignment with the mission scenario, this instrument is housed in a modular payload box that can be attached to the robotic arm of the Lightweight Rover Unit 2 (LRU2), allowing the rover to use the instrument autonomously in the field. A compact Nd:YAG laser is utilized for material ablation, generating a micro-plasma that is subsequently analyzed with a small fiber-coupled spectrometer. A single-board computer controls the LIBS hardware components for data acquisition. In this study, we provide details of the ARCHES LIBS instrument implementation, report on preceding laboratory tests where the LRU2 operated the LIBS module for the first time, and showcase the results obtained during the successful ARCHES space analogue demonstration mission campaign in summer 2022 in Sicily.