Since its initial discovery, four decades ago, transition metal bifluoride chemistry has exhibited a slow growth, mainly due to problems associated with synthesis and characterization. Until recently, reports on this chemistry almost always presented these complexes as a fluke discovery. However, with the recent increase in reports and applications involving such species, a renewed interest in these complexes has been observed. Most of the work done in this area, so far, has been directed toward the synthesis and quite challenging characterization of these complexes, yet mostly neglecting the behavior of such species and their influence on catalytic processes. The aim of this work is to present a summary of the various preparation methods, characterization techniques and applications of reported transition metal bifluoride complexes. It is our hope that by centralizing all information available on such species, future efforts aimed at exploiting the full potential of transition metal bifluoride species can be facilitated.