We exploited the exceptional thermal stability and diverse molecular shapes of higher diamondoids (C22 and higher polymantanes) to isolate them from petroleum. Molecules containing 4 to 11 diamond-crystal cages were isolated and crystallized, and we obtained single-crystal x-ray structures for representatives from three families. Rigidity, strength, remarkable assortments of three- dimensional shapes, including resolvable chiral forms, and multiple, readily derivatizable attachment sites make them valuable nanometer-size molecular building blocks.