Soft x-ray fluorescence spectroscopy provides an element and angular momentum selective measure of the valence band density of states in complex materials. Results are presented demonstrating the use of SXF both as a means of solving materials problems and as a means of increasing our fundamental understanding of low energy excitation processes in various types of materials. As examples of materials applications, we discuss the L2,3 spectra of Si in various environments, and describe radiation damage studies in Beryl. Fundamental new insights are provided by the study of SXF spectra excited near an x-ray threshold. For such excitation, recent work demonstrates that an electronic Raman scattering process can greatly modify the normal fluorescence spectrum. We discuss near threshold studies of graphite, h-BN and NiS to demonstrate that the nature of the electronic excitation processes differs dramatically in various classes of materials and provides important new insights into their properties.