The use of mass spectrometry (MS) based methods in organogold chemistry is reviewed. The focus is on both fundamental gas‐phase ion chemistry studies in which the mass spectrometer is used as a “gas‐phase reactor” and the analytical applications of mass spectrometry. For the former, the topics covered include: thermochemical measurements (bond energies from reactions of Au
+
with substrates and Au
+
and R
3
PAu
+
affinities); photoelectron, IR and UV‐Vis spectroscopy; ion‐molecule reactions of bare Au
+
, ligated Au(L)
n
+
, Au
−
and gold clusters with substrates; formation and reactions of organogold ions. The latter includes a discussion on: the use of different ionization methods (electron ionization, fast‐atom bombardment, electrospray ionization and matrix assisted laser desorption ionization) in the analysis of gold compounds; the use of MS in the bioinorganic chemistry of gold; MS‐based studies of relevance to catalysis.