The free-electron laser (FEL) has become an important tool for producing high-intensity photon beams, especially in the infrared. Synchrotron radiation's primary spectral domains are in the ultraviolet and X-ray region. FEL's are therefore excellent complimentary facilities to synchrotron radiation sources. While FEL's have seen only limited use in experimentation, recently developed programs at Vanderbilt University in Jashville, TN, are swiftly rectifying this situation. This review paper examines practical experience obtained through pioneering programs using the Vanderbilt FEL, which currently hosts one of the largest FEL materials research programs. Results will be discussed in three areas: two-photon absorption in germanium, FEL-assisted internal photoemission measurements of interface energy barriers (FELIPE), and wavelength-specific laser diamond ablation.