Soluble chalcogenido clusters together with transition metal ions and main group elements are shown to provide gels having interconnected, open frameworks. Following supercritical drying with liquid carbon dioxide, the chalcogels may be converted to aerogels. The aerogels possess high internal surface areas with a broad pore size distribution that is dependent upon the precursors used and the aging conditions applied. Some of the gels are encompassed by formulas such as M4[M′4Qx]n, M4[M′2Qy]n, M4[M′Qx]n, M3[M″Qx]n, or Me2[M′″Qx]n, where M is a divalent, trivalent, or tetravalent metal ion; M′, M″, and M′″ are typically Ge, Sn, P, As, Sb, Mo, or W; and Q is typically S, Se, or Te. Methods of preparing the chalcogenido clusters are also provided.