This chapter outlines spectroscopic techniques which are most commonly applied to complexes of the f-block elements. It describes electronic absorption, luminescence, Nuclear Magnetic Resonance (NMR) and electron paramagnetic resonance (EPR) spectroscopies. The chapter considers NMR spectroscopy of paramagnetic complexes, the applications of lanthanide shift reagents, NMR spectroscopy of lanthanide nuclei and the use of Gadolinium (Gd)3+ complexes as relaxation agents for NMR imaging. It discusses emission spectroscopy, which is an extremely sensitive technique. For most paramagnetic lanthanide and actinide complexes, strong spin-orbit coupling results in fast electron spin-lattice relaxation and their NMR spectra show reasonably sharp lines. Historically much of interest in NMR spectroscopy of paramagnetic lanthanide complexes has been due to their use as shift reagents to simplify NMR spectra of organic molecules. Most EPR studies of Gd3+ have been carried out on solid samples, and in order to extract the maximum amount of information, single crystals have been used to obtain information about crystal field strength and symmetry.