Apart from structure and composition, morphology plays a significant role in influencing the performance of materials in terms of both bulk and surface behavior. In this work, polylactic acid (PLA) constituted by submicrometric fibers is prepared. Using a modified electrospinning (ES) device to carry out solution blow spinning (SBS), the fibrillar morphology is modified, with the aim to induce variations in the properties of the material. The modification of the ES device consists of the incorporation of a source of pressurized gas (air) and a 3D-printed nozzle of our own design. For this work, the morphology of the PLA submicrometric fibers is modified by varying the rotational speed of the collector in order to understand its influence on different properties and, consequently, on the performance of the material. The rotational speed of a cylindrical collector (250, 500, 1000 and 2000 rpm) is considered as variable for changing the morphology. Morphological study of the materials was performed using scanning electron microscopy and image analysis carried out with ImageJ 1.54f software. Besides a morphology study, structural characterization by Fourier transformed infrared spectroscopy using attenuated total reflectance of prepared materials is carried out. Finally, the morphology and structure of produced PLA fibrous mats were correlated with the analysis of mechanical properties, wettability behavior and adhesion of DH5-α E. coli bacteria. It is of interest to highlight how small morphological and chemical structure variations can lead to important changes in materials’ performance. These changes include, for example, those above 30% in some mechanical parameters and clear variations in bacterial adhesion capacity.