This article presents, from amass spectrometry perspective, an historical account of research on gas-phase carbon clusters, which has led to the discovery of another form of carbon, fullerenes. In addition, more recent mass spectrometric studies on analysis of fullerene derivatives and synthesis of doped fullerenes are described. The early, strong evidence for certain "magic number" carbon clusters, most notably C60 (buckminsterfullerene), was obtained largely from mass spectrometric experiments. These studies led to the controversial postulation of the soccerball structure for C60, which provoked increased experimental and theoretical efforts. This research eventually resulted in the discovery of a simple method by which large quantities of fullerenes can be produced. The availability of these new, all-carbon molecules has motivated a broad range of synthetic and characterization studies that are expanding at a frenetic pace. Mass spectrometry not only played a critical role in the discovery of fullerenes but also now is crucial for determination of the unusual chemical and physical properties of fullerenes and fullerene-based materials.