The elucidation of the volatile profile of honey samples is critical both for the evaluation of their quality and for their classification according to their botanical and geographical origin [1-2]. In this work, solid-phase microextraction Arrow (SPME Arrow) combined with comprehensive two- dimensional gas chromatography – mass spectrometry (GC×GC-MS) was used for the first time for the exploration of the volatile profile of honey samples. Due to the significantly higher sorption phase of SPME Arrow in comparison with conventional SPME fibers, the utilization of this technique results in enhanced sensitivity [3]. At the same time, GC×GC-MS serves as a powerful analytical tool for untargeted analysis due to its high sensitivity, selectivity, and peak capacity [4]. The main parameters that could potentially affect the extraction efficiency were optimized. Under optimum conditions, extraction was performed using divinylbenzene/polydimethylsiloxane (DVB/PDMS) SPME Arrow fibers and adsorption of the target analytes was carried out at 50 oC for 50 min under constant stirring. As a proof-of-concept, the proposed method was successfully employed for the analysis of multifloral and unifloral secretion and flower honey samples. The combination of GC×GC- MS and Arrow SPME enabled the determination of more than 200 compounds of different chemical classes including aldehydes, ketones, furanic compounds, and terpenes. [1] L. Piasenzotto, L. Gracco, L. Conte, Solid phase microextraction (SPME) applied to honey quality control, J. Sci. Food Agric. 83 (2003) 1037–1044. [2] P.M. Da Silva, C. Gauche, L.V. Gonzaga, A.C.O. Costa, R. Fett, Honey: Chemical composition, stability and authenticity, Food Chem. 196 (2016) 309–323. [3] N. Manousi, E. Rosenberg, G.A. Zachariadis, Solid-phase microextraction arrow for the sampling of volatile organic compounds in milk samples, Separations. 7 (2020) 75. [4] G. Dugo, F.A. Franchina, M.R. Scandinaro, I. Bonaccorsi, N. Cicero, P.Q. Tranchida, L. Mondello, Elucidation of the volatile composition of marsala wines by using comprehensive two-dimensional gas chromatography, Food Chem. 142 (2014) 262–268.