A family of cesium-germanium halide salts have utility as nonlinear optical crystals in applications including electro-optics and optical frequency conversion. These salts have the general formula CsGeCl.sub.x Br.sub.y I.sub.z, in which x, y, and z equal 0 through 3, inclusive, and where x+y+z=3. In contrast to well-known oxygen-containing materials, such as LiNbO.sub.3, these cesium-germanium halide salts exhibit optical nonlinearity with an extremely wide transparency range (without significant absorption) at wavelengths from about 0.4 .mu.m to greater than 25 .mu.m (covering the entire MWIR and LWIR regions). Based on Ge.sup.2+ ions, these halides have non-centrosymmetric perovskite structures. The halide ions form a strongly coordinating octahedral environment about the Ge.sup.2+ ions and resist migration in an electric field. The Ge2+ ions, however, are shifted slightly off center in the tetragonal phase, leading to a net electric dipole moment in each unit cell. The alignment of these dipole moments into ferroelectric domains can be controlled through applied electric fields. By aligning all dipole moments into a single ferroelectric domain, these cesium-germanium halides have utility for electro-optic and birefringently phase-matched frequency conversion devices. Alternately, periodic poling of the ferroelectric domains allows these materials to be used for quasi-phase-matched frequency conversion. Cesium-germanium halide salts, which can be isolated from aqueous solutions as salts of GeX.sub.3 .sup.- anions, are water-soluble, which facilitates large-aperture crystal growth.