We have obtained or retrieved IUE spectra for over 100 middle- and late-type giant and supergiant stars whose spectra indicate the presence of a hot component earlier than type F2. The hot companions are classified accurately by temperature class from their far-UV spectra. The interstellar extinction of each system and the relative luminosities of the components are derived from analysis of the UV and optical fluxes, using a grid of UV intrinsic colors for hot dwarfs. We find that there is fair agreement in general between current UV spectral classification and ground-based hot component types, in spite of the difficulties of assigning the latter. There are a few cases in which the cool component optical classifications disagree considerably with the temperature classes inferred from our analysis of UV and optical photometry. The extinction parameter agrees moderately well with other determinations of B-V color excess. Many systems are worthy of further study especially to establish their spectroscopic orbits. Further work is planned to estimate luminosities of the cool components from the data herein; in many cases, these luminosities' accuracies should be comparable to or exceed those of the Hipparcos parallaxes.