Microbial volatile organic compounds (MVOCs) are present in several production processes in biotechnology. In this study it is evaluated the viability of use of a method involving solidphase microextraction (SPME), in vivo SPME, in the extraction of MVOCs, associated with the pigment production process by the Monascus fungus. PDMS/Car/DVB (50/30 μm) fiber in the headspace mode (HS-SPME) and gas chromatography-mass spectrometry (GC-MS) were used to fermentation broth study. Seventeen compounds were found associated with the presence of the fungus, being the main ones ethanol, 2-methyl-propanol, 3-methyl-butanol, 2-methyl-butanol and 2-phenyl-ethanol. These compounds have maximum concentration of 313.87, 5.51, 2.37, 0.95 and 0.70 mg L −1 . The values of biomass and red pigment found for fermentation for ten days were 4.03 ± 0.21 g L −1 and 3.96 ± 0.17 (UA 480 ). Regular MVOC productions were observed in this study, which were useful in the prediction and control of fermentation by Monascus fungus.