This study presents a new, user-friendly, cost-effective and portable headspace solid-phase extraction technique based on graphene oxide decorated with iron oxide magnetic nanoparticles as sorbent, located on one end of a small neodymium magnet. Hence, the new headspace solid-phase extraction technique has been called Magnetic Headspace Adsorptive Extraction (Mag-HSAE). In order to assess Mag-HSAE technique applicability to model analytes, some chlorobenzenes were extracted from water samples prior to gas chromatography-mass spectrometry determination. A multivariate approach was employed to optimize the experimental parameters affecting Mag-HSAE. The method was evaluated under optimized extraction conditions (i.e., sample volume, 20 mL; extraction time, 30 min; sorbent amount, 10 mg; stirring speed, 1500 rpm, and ionic strength, non-significant), obtaining a linear response from 0.5 to 100 ng L for 1,3-DCB, 1,4-DCB, 1,2-DCB, 1,3,5-TCB, 1,2,4-TCB and 1,2,3-TCB; from 0.5 to 75 ng L for 1,2,4,5-TeCB, and PeCB; and from 1 to 75 ng L for 1,2,3,4-TeCB. The repeatability of the proposed method was evaluated at 10 ng L and 50 ng L spiking levels, and coefficients of variation ranged between 1.5 and 9.5% (n = 5). Limits of detection values were found between 93 and 301 pg L. Finally, tap, mineral and effluent water were selected as real water samples to assess method applicability. Relative recoveries varied between 86 and 110% showing negligible matrix effects.