The synthesis of efficient and low-cost coatings for solid-phase microextraction attracted much attention. Conductive polymers are excellent candidates for this purpose due to the possibility of electropolymerization, which results in the reproducible synthesis of films. A plethora of studies reported in the literature concluded that modification of conductive polymers with innovative materials could lead to an increase in sensitivity toward specific analytes. In this work, the metal–organic framework-polypyrrole composite was electrodeposited in one step directly onto a stainless-steel substrate. The effect of synthesis parameters on extraction efficiency was investigated. The obtained PPy@ZIF-8 coating was subjected to physical–chemical characterization using electron microscopy and Fourier-transform IR spectroscopy. The main finding of the study was that the values of the limit of detection and intra- and inter-day reproducibility for analytes with different chemical structures were found to be lower as compared to pure polypyrrole coating. Furthermore, the obtained polypyrrole-MOF coating was applied for the collection of profiles of volatile organic compounds liberated by bacteria. Hence, the polypyrrole@ZIF-8 coating synthesized using a low-cost and facile approach presented in this study can be useful for the profiling of VOCs liberated by bacteria.