2.2.2-Cryptand(1+) salts of the [Sb2Se4](2-), [As2S4](2-), [As10S3](2-), and [As4Se6](2-) anions have been synthesized from the reduction of binary chalcogenide compounds by K in NH3(l) in the presence of the alkali-metal-encapsulating ligand 2.2.2-cryptand (4,7,13,16,21,24-hexaoxa-1,10-diazabicyclo[8.8.8]hexacosane), followed by recrystallization from CH3CN. The [Sb2Se4](2-) anion, which has crystallographically imposed symmetry 2, consists of two discrete edge-sharing SbSe3 pyramids with terminal Se atoms cis to each other. The Sb-Se-t bond distance is 2.433(1)Angstrom, whereas the Sb-Se-b distance is 2.615(1) Angstrom (t = terminal; b = bridge). The Se-b-S-b-Se-t angles range from 104.78(4) to 105.18(5)degrees, whereas the Se-b-Sb-Se-b angles are 88.09(4) and 88.99(4)degrees. The Se-77 NMR data for this anion in solution are consistent with its X-ray structure (delta 337 and 124 ppm, 1:1 intensity, -30 degrees C, CH3CN/CD3CN). Similar to this [Sb2Se4](2-) anion, the [As2S4](2-) anion consists of two discrete edge-sharing AsS3 pyramidal units. The As-S-t bond distances are 2.136(7) and 2.120(7) Angstrom, whereas the As-S-b distances range from 2.306(7) to 2.325(7) Angstrom.