Calibration-free methods in laser-induced breakdown spectroscopy, CF LIBS, serve as an alternative to calibration-based LIBS techniques. Their major advantage is the ability for fast chemical analysis in situations where matrix-matched standards are not readily available (e.g., in the analysis of biological materials and remote analysis) or amounts of samples are limited. Their main applications are in the industry, geology, biology, archeology, and even space exploration. This chapter overviews the principle of operation and performance of CF LIBS techniques.