This review summarizes literature data from the past 5 years on new developments and/or applications of sample preparation methods for analysis of volatile organic compounds (VOC), mainly in air and water matrices. Novel trends in the optimization and application of well-established airborne VOC enrichment techniques are discussed, like the implementation of advanced cooling systems in cryogenic trapping and miniaturization in adsorptive enrichment techniques. Next, focus is put on current tendencies in integrated sampling-extraction-sample introduction methods such as solid phase microextraction (SPME) and novel in-needle trapping devices. Particular attention is paid to emerging membrane extraction techniques such as membrane inlet mass spectrometry (MIMS) and membrane extraction with a sorbent interface (MESI). For VOC enrichment out of water, recent evolutions in direct aqueous injection (DAI) and liquid-liquid extraction (LLE) are highlighted, with main focus on miniaturized solvent extraction methods such as single drop microextraction (SDME) and liquid phase microextraction (LPME). Next, solvent-free sorptive enrichment receives major attention, with particular interest for innovative techniques such as stir bar sorptive extraction (SBSE) and solid phase dynamic extraction (SPDE). Finally, recent trends in membrane extraction are reviewed. Applications in both immersion and headspace mode are discussed.