AbstractThere has been tremendous interest in the use of alkyltrioxorhenium complexes as catalysts for various organic transformations. Although such applications are now well known and, indeed, have been widely studied, other organorhenium oxide families, namely the perrhenate esters O3ReOR, have received much less attention. In this review, such ReVII species are shown to be very promising catalysts and several recent examples are presented, with the aim of shedding light on their synthetic potential as a new tool for organic chemists.