The hypothesis that high temperature, reduction atmophere pyrotechnology was evolved by potters in Southeast Europe before its adoption by late Neolithic metallurgists is examined in this paper. Pottery samples representing the range of compositional and contextual variability in the ceramic assemblages of two Vinca culture sites in Yugoslavia are analyzed in terms of their firing temperatures by means of thermal expansion and scanning electron microscopy. It is shown that the Vinca potters were able to achieve temperatures averaging 975° in conjunction with reducing atmosphere on a routine basis prior to the first appearance of copper ore processing in later Vinca sites.