Metal-organic frameworks as porous materials are highly advantageous over other porous carriers like mesoporous silica or zeolites. They provide advantages for biomolecule release and their adsorption characteristics offer many opportunities. Thus, they present high applicability in medicine and biology. Metal-organic frameworks (MOF) possess appealing structures and usages including high surface area, homogenous structured nanoscale cavities, and excellent thermal stability. Therefore, they can be a new sorbent alternative for preparing samples. In the present study, a MOF fiber application for solid-phase microextraction is reported. The MOF fiber is in nano size and has a high surface area. 3D and oriented organizations of MOF materials are vital so that they may be utilized as the fiber coating for microextraction in solid-phase for volatile substances in the medicinal herbs. In order to make Cu-based MOFs into three-dimensional hierarchical nanoarray structures, a coordination replication approach is created. To this end, Cu(OH)2 nanorod arrays are used as a sacrificial template. Cu(OH)2 nanorod arrays serving as Cu origin provided coordination with organic ligands for forming MOF crystals and 3D substrate for supporting Cu-based MOF growth. Following the presentation of the fiber, essential oils of Satureja hortensis L were determined using GC-MS. Ease of use, shorter analysis period, inexpensive tools as well as a high rate of recovery are advantages of the proposed approach compared to ordinary analysis approaches.