Two different high-pressure and-temperature synthetic routes have been used to produce only the second-known pentavalent CaIrO3-type oxide. Postperovskite NaOsO3 has been prepared from GdFeO3-type perovskite NaOsO3 at 16 GPa and 1135 K Furthermore, it has also been synthesized at the considerably lower pressure of 6 GPa and 1100 K from a precursor of hexavalent Na2OsO4 and nominally pentavalent KSbO3-like phases. The latter synthetic pathway offers a new lower-pressure route to the postperovskite form, one that completely foregoes any perovskite precursor or intermediate. This work suggests that postperovskite can be obtained in other compounds and chemistries where generalized rules based on the perovskite structure may not apply or where no perovskite is known. One more obvious consequence of our second route is that perovskite formation may even mask and hinder other less extreme chemical pathways to postperovskite phases.