The hexacyanotitanate salt, [Et4N](3)[Ti(CN)(6)]. 4MeCN, has been prepared by addition of tetraethylammonium cyanide to the titanium(III) triflate salt Ti(O3SCF3)(3)(MeCN)(3). The orange crystalline product has been characterized by X-ray diffraction, and the d(1) anion is only slightly distorted from ideal O-h symmetry. The anion resides on a center of symmetry and is characterized by the following parameters : Ti-C = 2.195(2), 2.197(3), and 2.213(3) Angstrom; C-N (av)= 1.141(4) Angstrom; C-Ti-C (cis) = 88.01(9), 88.02(9), 89.02(9), and 89.78(9)degrees; C-Ti-C (trans)= 180 degrees. In addition to the crystallographic study, details of the IR (nu(CN) = 2071 cm(-1)), EPR, and UV-vis spectra (Delta(0) = 22800 cm(-1)) are given. Crystal data for [Et4N](3)[Ti(CN)(6)]. 4MeCN are as follows : monoclinic, space group I2/a, a = 18.171(6) Angstrom, b = 12.200(4) Angstrom, c = 20.989(5) Angstrom, beta = 91.17(2)degrees, V = 4652(2) Angstrom(3), Z = 4, wR(2) = 0.2054 for 3831 data, 27 restraints, and 318 parameters.