2-Substituted oxazolo[3,2-a]pyridinium salts have been synthesised starting from the appropriate 2-(4-ethoxybutyryl) oxazoles, which are treated with hydrobromic acid and then cyclised and aromatised by boiling acetic anhydride. Attempts to synthesise 2- substituted oxazoles suitable for the synthesis of the parent oxazolopyridinium salt were not successful. Catalytic reduction of two oxazolopyridinium salts leads to ring opening giving N-substituted-2-piperidones. Attempts to prepare the parent isoxazolo[2,3-a]pyridinium ion by the same route have led to the isolation of a compound of unknown structure. The reactions and properties of this compound have been investigated and proposed structures are discussed. The first synthesis of a substituted isoxazolo[2,3-a]pyridinium salt is reported using a synthetic route that involves the elimination of hydrogen bromide from the appropriate α,α-dibromoketone.