Preconcentration for on-site detection or subsequent determination is a promising technique for selective sensing explosive markers at low concentrations. Here, we report divinylbenzene monolithic polymer in its blank form (neat-DVB) and as a composite incorporated with sodalite topology zeolite-like metal-organic frameworks (3-ZMOF@DVB), as a sensitive, selective, and cost-effective porous preconcentrator for aliphatic nitroalkanes in the vapor phase as explosive markers at infinite dilution. The developed materials were fabricated as 18 cm gas chromatography (GC) monolithic capillary columns to study their separation performance of nitroalkane mixture and the subsequent physicochemical study of adsorption using the inverse gas chromatography (IGC) technique. A strong preconcentration effect was indicated by a specific retention volume adsorption/desorption ratio equal to 3 for nitromethane on the neat-DVB monolith host-guest interaction, and a 14% higher ratio was observed using the 3-ZMOF@DVB monolithic composite despite the low percentage of 0.7 wt.% of sod-ZMOF added. Furthermore, Incorporating ZMOF resulted in a higher percentage of micropores, increasing the degree of freedom more than bringing stronger adsorption and entropic-driven interaction more than enthalpic. The specific free energy of adsorption (ΔGS) values increased for polar probes and nitroalkanes, denoting that adding ZMOFs earned the DVB monolithic matrix a more specific character. Afterward, Lewis acid-base properties were calculated, estimating the electron acceptor (KA) and electron donor (KB) constants. The neat-DVB was found to have a Lewis basic character with KB/KA = 7.71, and the 3-ZMOF@DVB had a less Lewis basic character with KB/KA = 3.82. An increased electron-accepting nature can be directly related to incorporating sod-ZMOF into the DVB monolithic matrix. This work considers the initial step in presenting a portable explosives detector or preconcentrating explosive markers trace prior to more sophisticated analysis. Additionally, the IGC technique allows for understanding the factors that led to the superior adsorption of nitroalkanes for the developed materials.