Due to a small number of components CuZrAl alloys often serve as model systems for investigations of bulk glass formation from the supercooled liquid state. On the other hand, CuZrAl glasses are suitable for studies of (partial) devitrification and formation of glass-matrix composites. The latter have been shown to exhibit superior mechanical properties, compared to the glass, in particular rather high yield strength and notable plasticity. In this contribution, a relationship between the structure of CuZrAl glasses and composites and their properties will be discussed. The structural investigations include X-ray, neutron and electron diffraction techniques, X-ray absorption spectroscopy as well as reverse Monte-Carlo and molecular dynamics simulations.