Reviewed in brief are the selected results of the application of headspace solid-phase microextraction as a preparative approach for gas chromatography – mass spectrometry (HS-SPME/GC-MS) for natural organic compounds research at the University of Split, Faculty of Chemistry and Technology. A wide variety of headspace compounds from different natural sources has been identified: lower aliphatic compounds (e.g., C5- and C6-compounds), aromatic compounds, monoterpenes (e.g., linalool derivatives (oxides, anhydro-oxides, epoxides), hotrienol), sesquiterpenes (e.g., eudesmol isomers, hydrocarbons), and C9- and C13-norisoprenoids (e.g., 3,4-dihydro-3-oxoedulan, 4-oxoisophorone, trans-β-damascenone). These compounds are important phytochemicals as flavour/fragrance compounds, chemical markers of the botanical origin or others (e.g., allelochemicals, pheromones, or acaricide residue).; Ukratko su prikazani odabrani rezultati primjene mikroekstrakcije vršnih para na čvrstoj fazi kao preparativnog pristupa plinskoj kromatografiji – spektrometriji masa (HS-SPME/GC-MS) za istraživanje prirodnih spojeva, koje je provedeno na Kemijsko-tehnološkom fakultetu Sveučilištu u Splitu. Velika raznolikost spojeva vršnih para istražena je iz različitih prirodnih izvora: niži alifatski spojevi (npr. C5- i C6-spojevi), aromatski spojevi, monoterpeni (npr. derivati linaloola (oksidi, anhidro-oksidi, epoksidi), hotrienol), seskviterpeni (npr. eudezmol izomeri, ugljikovodici) te C9- i C13-norizoprenoidi (npr. 3,4-dihidro-3-oksoedulan, 4-oksoisoforon, trans-β-damascenon). Ti su spojevi važne fitokemikalije kao spojevi aroma/mirisa, kemijski marker botaničkog podrijetla ili drugo (npr. aleokemikalije, feromoni ili ostatci akaricida).