Fullerenes and various chlorinated carbon clusters were synthesized via the glow discharge reaction using chloroform vapor as starting reactant. High-performance liquid chromatography combined with ultraviolet spectrometry and mass spectrometry (HPLC--UV--MS) was developed for separation and characterization of the reaction products, comprising C-60 and C-70 fullerenes, amorphous carbon, and more than 50 chlorinated carbon clusters, which molecular formulas were determined from their special isotopic patterns. The formation of fullerenes and amorphous carbon in the glow discharge reaction of chloroform was found to involve different systems of chlorinated carbon cluster intermediates. The correlation provides insight into the formation of fullerenes and the other carbon clusters.