Both electron paramagnetic resonance (EPR) and electron nuclear double resonance (ENDOR) spectroscopies are extremely powerful and versatile methods for the characterisation of paramagnetic systems in biology, chemistry, and physics. However, by comparison to EPR, ENDOR remains a less widely used technique. In this tutorial review the basic principles of continuous wave ENDOR are described. The theory of orientation selective ENDOR, for structure determination in frozen solutions and powders, is then described. A range of examples, illustrating the type of information obtained from the ENDOR spectrum, is finally presented.