Solid-phase microextraction (SPME) is widely used in analytical laboratories for the analysis of organic compounds, thanks to its simplicity and versatility. However, the current commercially available fibers are based on nonselective sorbents, making difficult in some cases the final determination of target compounds by chromatographic techniques. Molecularly imprinted polymers (MIPs) are stable polymers with selective molecular recognition abilities, provided by the template used during their synthesis. In the present work, a simple polymerization strategy allowing the obtainment of molecularly imprinted polymeric fibers to be used in SPME is proposed. Such a strategy is based on the direct synthesis of molecularly imprinted polymeric fibers (monoliths) using silica capillaries as molds, with silica being etched away after polymerization. The system propazine:methacrylic acid was used as a model for the preparation of molecularly imprinted fibers, and its ability to selectively rebind triazines was evaluated. Variables affecting polymer morphology (i.e., polymerization time, fiber thickness) and binding-elution of target analytes (i.e., solvents, time, temperature) were studied in detail. The imprinted fiber showing the best performance in terms of selectivity and affinity for triazines was successfully applied to the extraction of target analytes from environmental and food samples.