Laser-induced breakdown spectroscopy (LIBS) is a promising elemental analysis technique that has rapidly evolved in numerous fields, including biomedical research and medical sciences, over the last two decades. In combination with other methods, it has the potential to examine complex biological structures and their species distributions. The present work first develops the basic understanding of LIBS and then reviews its evolution in oncological diagnosis and calcified tissue analysis from medical perspectives over the last 11 years. LIBS can potentially improve early cancer detection and monitor treatment outcomes, ultimately enhancing patient care and diagnosis. It has effectively differentiated between malignant and normal tissues and also classifies cancer stages and types based on disease severity. Its applications for categorising and identifying calcified tissues are attractive for inspecting minerals, while soft tissue is more challenging, given the potential for significant matrix effects. This review article deals with the following aspects of LIBS and its application: (i) the fundamentals of this analytical measurement method, (ii) the matrix effect and its influence on the LIBS analyses of various biological tissues, (iii) the role of signal enhancement methodologies and artificial intelligence models to advance the method for analyses of biological sample materials, and (iv) applications of LIBS in cancer and calcified tissues investigations. This article also addresses challenges and opportunities encountered in these applications and discusses prospects, providing a comprehensive overview of the current state and potential advancement in LIBS technology.