<p>Laser-Induced Breakdown Spectroscopy (LIBS) is a robust and versatile analytical technique for elemental analysis, commonly used for remote analysis in hazardous environments by leveraging a pulsed laser to generate plasma and detect characteristic spectral lines. LIBS has become a critical tool for rapid, in-situ analysis across diverse fields. Despite its advantages, LIBS faces inherent limitations, including low sensitivity and suboptimal detection limits. This review critically examines advancements in LIBS enhancement techniques, mainly focusing on applying external electrostatic fields and pre-heated targets. These techniques are widely adopted due to their simplicity, cost-effectiveness, and significant impact on LIBS performance. Applying an external electric field modifies plasma properties, enhancing spectral emission through increased electron density, temperature, and excitation states. Meanwhile, target pre-heating improves ablation rates, reduces surface reflectivity, and enhances plasma emission intensity by up to 6000%. The review comprehensively explores various experimental setups, including diverse electric field configurations and pre-heating methods. It analyses their effects on emission characteristics across different material classes, including metals and semiconductors. These findings underscore the potential of electric field-assisted and thermally enhanced LIBS in environmental monitoring, metallurgy, biomedical diagnostics, and industrial quality control, offering a pathway toward more sensitive and accurate elemental analysis.</p>