A new technique for solid-phase microextraction (SPME) of analytes using a helical solid sorbent followed by thermal desorption into a gas chromatographic injector is reported. The main factors that affect the mass transport of analytes in sorption and thermal desorption process using a poly(dimethylsiloxane) (PDMS) helical sorbent are described. The sorption and thermal desorption were achieved in a few seconds, being very close by the theoretical prediction. Both processes were very fast by the reduction of the thickness of boundary layer between sorbent and gaseous sample as a result of a turbulent rotational flow of the headspace air on the surface of sorbent, which is generated by the helical configuration of the sorbent. The thermal desorption was also reduced by improving heat transfer into a thin boundary layer and by increasing the temperature of the heat transporter (carrier gas). The sorption and desorption with PDMS helical sorbent were compared with those of the PDMS silica rod. The extraction time was as much as 15 times faster with the PDMS helical sorbent than with the PDMS silica rod. The desorption with the PDMS helical sorbent was very fast, giving narrow peaks without tailing and a high efficiency of separation in comparison with PDMS silica rod.