Laser-Induced Breakdown Spectroscopy (LIBS)technology, a type of atomic emission spectrometry analysis that utilizes a laser as an excitation source, has undergone rapid development in recent years owing to its rapid, in-situ, multi-element detection capabilities and minimal sample preparation. Although its sensitivity is generally lower than that of inductively coupled plasma mass spectrometry (ICP-MS) and some other techniques, LIBS—by virtue of its deployment flexibility, portability, and the foregoing attributes—is better suited to online monitoring. This work summarizes the latest research progress of LIBS in the field of real-time monitoring and provides a comprehensive comparative analysis of the strengths and weaknesses of LIBS relative to XRF, ICP-MS, and other related techniques, specifically focusing on industrial raw material/product quality control during manufacturing, in situ elemental analysis during laser processing, and environmental pollutant emissions tracking. Across these applications, LIBS exhibits variable detection stability and sensitivity: in industrial settings, relative standard deviations (RSDs) typically remain below 15% (with minor elements reaching 15–30%), while detection limits (LODs) predominantly range at ppm levels (with limited ppb-level achievements). Environmental monitoring shows RSDs heavily dependent on instrumentation and field conditions, with reported LODs spanning ng/m3 to mg/m3 (air pollutants), μg/L to mg/L (water quality), and mg/kg (soil analysis). This work also explores the practical challenges encountered during the implementation of LIBS across various domains. In the industrial sector, the primary obstacles involve suboptimal detection accuracy and stability, stemming from high solid-surface complexity, the difficulties of liquid metal analysis, contamination of metallurgical molds, and harsh operating environments. Within the field of laser processing, the challenges mainly arise from the instability of the welding molten pool and the ambiguity in defining thresholds for determining the extent of machining. Conversely, environmental monitoring is primarily constrained by relatively low sensitivity when analyzing gaseous and liquid states. Finally, targeted solutions corresponding to the specific technical challenges in each field are proposed. Future developments in signal enhancement are anticipated to overcome current technical constraints, enabling robust high-sensitivity, multi-element detection in complex sample systems.