Calibration-free laser-induced breakdown spectroscopy (LIBS) offers an innovative method for the elemental analysis, providing benefits that surpass cumbersome sample preparations and costly, time-consuming traditional calibration-based approaches. By avoiding the requirement for extensive calibration-based measurements, this method simplifies analysis procedure, thereby making it especially attractive for the rapid test sample analysis. This chapter explores the fundamental principles of calibration-free LIBS, shedding light on its procedure, and self-absorption corrections, and probing its diverse range of applications. Examining diverse real-life LIBS applications uncovers the flexibility of calibration-free LIBS in various applications such as spanning environmental monitoring, determining quality of food products, herbal medicinal plants as well as soil nutrient analysis, and evaluating water contaminants, concrete corrosion estimation, and agricultural plant studies. This chapter also covers the capabilities and limitations of the CF-LIBS concept in detail, as well as the various CF-LIBS variants and algorithms involved. In addition, the common LIBS technique issues are also covered in this chapter along with practical, realistic solutions as well as few real-world applications.