Preparation of a molecularly imprinted carbon is described. The molecularly imprinted carbon has a surface that is imprinted on the molecular level for a specific template molecule of interest, making it highly selective for analytes corresponding to at least a portion of the template molecule. Devices including the molecularly imprinted carbon and their use in methods of detecting analytes are also described. As an example, dibutyl butylphosphonate (DBBP), a surrogate for chemical warfare agents, was used as a template molecule. Electrospun molecularly imprinted SU-8 and pyrolyzed polymer (PP) solid-phase microextraction (SPME) devices were prepared; their ability to preferentially extract DBBP from an aqueous matrix, with and without interferences present, was evaluated via comparison with non-imprinted SU-8 and PP SPME fibers. The electrospun devices demonstrated a higher selectivity for DBBP, as evidenced by their extraction time profiles. The MI-SPME fibers tested extracted at least 60% more DBBP than their non-imprinted counterparts.