The electrocrystallization of tetraphenylphosphonium and tetraphenylarsonium halide double salts of the C60-and C70- fulleride anions has been investigated. The mechanism of precipitation, growth of single crystals and application to separation and generation of various reduced states of the fullerenes are discussed. Electro-chemical methods have demonstrated an initial dissolution-precipitation mechanism exhibiting a high level of supersaturation, followed by growth of a solid phase of low solubility in 1,2-dichlorobenzene. Single crystals with at least 400 mum face dimensions have been grown Methods for generation of fluxes of either the doubly charged anions or of the fullerene precursors from the salts are described.