► The development of parametric down-conversion devices operating from 3 to about 20 μm is reviewed. ► All time scales, from continuous wave to femtosecond regime, are considered. ► An overview of the available non-oxide mid-infrared nonlinear optical materials is also included. The development of parametric down-conversion devices operating in the mid-infrared, from 3 μm to about 20 μm, based on non-oxide nonlinear optical crystals is reviewed. Such devices, pumped by solid-state laser systems operating in the near-infrared, fill in this spectral gap where no solid-state laser technology exists, on practically all time scales, from continuous-wave to femtosecond regime. The vital element in any frequency-conversion process is the nonlinear optical crystal and this represents one of the major limitations with respect to achieving high energies and average powers in the mid-infrared although the broad spectral tunability seems not to be a problem. Hence, an overview of the available mid-infrared nonlinear optical materials, emphasizing new developments like wide band-gap, engineered (mixed), and quasi-phase-matched crystals, is also included.