A chemical vapor deposition (CVD) process for preparing electrical and optical chalcogenide materials. In a preferred embodiment, the instant CVD-deposited materials exhibit one or more of the following properties: electrical switching, accumulation, setting, reversible multistate behavior, resetting, cognitive functionality, and reversible amorphous-crystalline transformations. In one embodiment, a multilayer structure, including at least one layer containing a chalcogen element, is deposited by CVD and subjected to post-deposition application of energy to produce a chalcogenide material having properties in accordance with the instant invention. In another embodiment, a single layer chalcogenide material having properties in accordance with the instant invention is formed from a CVD deposition process including three or more deposition precursors, at least one of which is a chalcogen element precursor. Preferred materials are those that include the chalcogen Te along with Ge and/or Sb.