The term junction spectroscopy embraces a wide range of techniques used to explore the properties of semiconductor materials and semiconductor devices. In this tutorial review we describe the most widely used junction spectroscopy approaches for characterizing deep-level defects in semiconductors and present some of the early work on which the principles of today's methodology are based. We outline ab-initio calculations of defect properties and give examples of how density functional theory in conjunction with formation energy and marker methods can be used to guide the interpretation of experimental results. We review recombination, generation and trapping of charge carriers associated with defects. We consider thermally driven emission and capture and describe the techniques of Deep Level Transient Spectroscopy (DLTS), high resolution Laplace DLTS, admittance spectroscopy and scanning DLTS. For the study of minority carrier related processes and wide gap materials we consider Minority Carrier Transient Spectroscopy (MCTS), Optical DLTS (ODLTS and DLOS) together with some of their many variants. Capacitance, current and conductance measurements enable carrier exchange processes associated with the defects to be detected. We explain how these methods are used in order to understand the behaviour of point defects, the determination of charge states and negative-U (Hubbard correlation energy) behaviour. We provide, or reference, examples from a wide range of materials including Si, SiGe, GaAs, GaP, GaN, InGaN, InAlN and ZnO.