This work is an overview about the diversity, specify, function/ecological roles and applications of microbial volatile organic compounds (mVOCs). i) The first database of microbial volatiles was established. ii) The role of mVOCs in skin microbial interactions and defences was investigated in detail and the result revealed new natural compounds released by Staphylococcus schleiferi isolates. These compounds influence the growth and phenotypes of bacteria, highlighting the role of mVOCs in skin microbe interactions and suggesting their implication in skin microbiota modulation and stability.