Comparison of electrospray LC–MS, LC–MS with Cold EI and GC–MS with Cold EI for sample identification

•Electrospray LC–MS, LC–MS with Cold EI and GC–MS with Cold EI are compared in their sample identification capabilities.•Reserpine and agidol 40 that are incompatible with standard GC–MS analyses are analyzed by GC–MS with Cold EI.•LC–MS with Cold EI and GC–MS with Cold EI have broader range of small molecules amenable for analysis than ESI–LC–MS.