Table grapes (Vitis vinifera) are affected by botrytis bunch rot and summer bunch rot, the latter a complex disease caused by Botrytis cinerea, Aspergillus spp., Penicillium expansum and Rhizopus stolonifer. To search for biocontrol alternatives, a new bioproduct composed of Gluconobacter cerinus and Hanseniaspora osmophila, a consortium called PUCV-VBL, was developed for the control of fungal rots in table grapes. Since this consortium presents new biocontrol species, the effect of their VOCs (volatile organic compounds) was evaluated under in vitro and in vivo conditions. The VOCs produced by the PUCV-VBL consortium showed the highest mycelial inhibition against Botrytis cinerea (86%). Furthermore, H. osmophila was able to inhibit sporulation of A. tubingensis and P. expansum. VOCs’ effect in vivo was evaluated using berries from Red Globe, Thompson Seedless and Crimson Seedless grapes cultivars, demonstrating a mycelial inhibition by VOCs greater than 70% for all evaluated fungal species. The VOC identification of the PUCV-VBL consortium was analyzed by solid-phase microextraction coupled to gas chromatography-mass spectrometry (SPME-GCMS). A total 26 compounds were identified, including 1-butanol 3-methyl, propanoic acid ethyl ester, ethyl acetate, phenylethyl alcohol, isobutyl acetate and hexanoic acid ethyl ester. Our results show that VOCs are an important mode of action of the PUCV-VBL biological consortium.