A system composed of ethylcellulose (EC) nanofibers loading with [5,10,15,20-tetrakis(pentafluorophenyl)porphyrinato]zinc(II) (TPPF 20 -Zn) was developed as electrospun mats to contribute to the inactivation of resistant bacteria strains. This tetrapyrrolic macrocycle was chosen for its excellent photostability and straightforward large-scale preparation, which are crucial attributes for practical applications. The synthesis and subsequent characterization of TPPF 20 -Zn demonstrated scalability and its ability to generate reactive oxygen species (ROS). Subsequently, nanofibrous mats based on EC loaded with different amounts of the porphyrin were obtained using the single-nozzle electrospinning technique after dissolution in a binary solvent mix of N,Ndimethylacetamide/ethanol. The fibers exhibited an adequate morphology at the nanoscale, a narrow diameter distribution, and an absence of beads. Additionally, the thermal and surface properties of the systems were analyzed, revealing no significant changes upon porphyrin incorporation. The developed electrospun composite nanofibrous mats demonstrated the capability to photokill Escherichia coli, as confirmed in planktonic suspension and using advanced fluorescence microscopy. Considering all the studies reported herein, we believe that the EC/TPPF 20 -Zn mats show promise for practical application in the field of antimicrobial patches or self-sterilizing surfaces.