The structural chemistry of nanoscale materials encapsulated within single-walled carbon nanotubes (SWNTs) is reviewed. SWNTs form atomically thin channels within a restricted diameter range, and their internal van der Waals surfaces regulate the growth behavior of encapsulated crystals in a precise fashion, leading to atomically regulated growth. The structural properties of these systems are largely dictated by the structural chemistry of the bulk material, although significant deviations from bulk structures are often observed, with lower surface coordinations and substantial lattice distortions.