Abstract New Zealand has some of the most active areas of rhyolitic volcanism in the world and this has produced numerous obsidian sources in the northern half of the North Island. In total archaeologists have recognized 27 named locations from which obsidian can be obtained scattered across 4 geological source regions. Shortly after colonization in the late 13th century AD Polynesian settlers began transporting this material some thousands of kilometers throughout the country and across the sea in small quantities to distant neighbors in the Kermadecs and Chatham islands. Although considerable research has been conducted on obsidian sourcing in New Zealand the complexity of geochemical source discrimination and the lack of a practical method of non-destructive geochemical analysis has hindered progress. We present the results of our use of PXRF to provide geochemical data on New Zealand obsidian sources and to compare the use of discriminant analysis and classification tree analysis to discriminate among sources and attribute archaeological samples to sources. Our research suggests that classification tree analysis is superior to discriminant analysis in sourcing studies. A large case study using an important settlement phase site (S11/20) from the Auckland region demonstrates the utility of the methods and the results support a model of high degrees of mobility and interaction during the early settlement of New Zealand.