The efficiency of a porous gold fiber used for solid-phase microextraction (PG-SPME) was investigated for the extraction of dodecanethiol out of ethanolic solution. A commercially available standard SPME (polydimethylsiloxane, carboxen, divinylbenzene-PDMS-Carb-DVB) was used as a reference to compare the extraction efficiency and selectivity of dodecanethiol with the PG-SPME fiber. The porous gold SPME fiber allowed the analysis of self-assembled monolayers on gold by gas chromatography-mass spectrometry (GC-MS). The PG-SPME fiber showed a five times higher peak area for dodecanethiol in GC-MS compared to the standard PDMS-Carb-DVB fiber. [Figure not available: see fulltext.]