The detection of chloride in reinforced concrete, crucial for maintenance against damage from de-icing salt or seawater, is advanced by Laser-Induced Breakdown Spectroscopy (LIBS). This study demonstrates that integrating microwaves with LIBS enhances cement analysis, improving the signal-to-noise ratio by up to four times and extending the detection limit for chlorine to 0.17 ± 0.02 wt%. As a method, microwave-enhanced LIBS (MWE-LIBS) has existed for a decade, but in cement analysis, MWE-LIBS has been used for the first time in Cl I atomic emission measurements. This pioneering approach provides a more efficient alternative, marking a significant advancement in cement analysis.