This paper focuses on laser-induced breakdown spectroscopy (LIBS) as an off-gas sensor and details a conceptual irradiation experiment to evaluate its performance in an environment that is more realistic of an operational molten salt reactor (MSR). MSRs are a promising advanced nuclear design that use high-temperature liquid salts as the coolant, fuel, or a combination of both. They will generate and subsequently evolve fission products into the reactor headspace during operation. These evolved fission products will necessitate an online off-gas system to treat the reactor cover gas before recycling it to the core. Such a system, especially during the early deployment phase, will benefit from online sensors to inform operators of the treatment system’s performance. Optical spectroscopy is well-suited to fit this task as it can be remotely deployed using fiber-optics and can detect most species at high frequencies. LIBS can detect nearly every element on the Periodic Table, stable or radioactive, making it an ideal candidate. The provided conceptual experiment discusses the facility requirements, salt capsule design, and detailed testing campaigns with corresponding simulated LIBS spectra.