The application of catheters to the urinary tract is associated with nosocomial infections. Such infections are one of the most common types of infections in hospitals and health care facilities and can lead to numerous medical complications. Therefore, the understanding of the properties of urinary catheter surfaces and their potential modifications are crucial in order to reduce bacterial adhesion and subsequent biofilm formation. In our study, we consider standard polyvinyl chloride (PVC) catheter surfaces and compare their properties with the properties of the same surfaces coated with poly(diallyldimethylammonium chloride)/poly(sodium 4-styrenesulfonate) (PDADMA/PSS) polyelectrolyte multilayers. Uncoated and coated surfaces were characterized by means of roughness, hydrophobicity, and zeta potential measurements. Finally, bacterial adhesion extent of uropathogenic Escherichia coli on bare and polyelectrolyte multilayer coated surfaces was measured. The obtained results show that on non-treated surfaces, biofilm is formed which was not the case for multilayer coated surfaces. The PSS-terminated multilayer shows the lowest bacterial adhesion and could be helpful in prevention of biofilm formation. The analysis of the properties of the uncoated and coated surfaces reveals that the most significant difference is related to the charge (i.e., zeta potential) of the examined surfaces, while roughness and hydrophobicity of the examined surfaces are similar. Therefore, it could be concluded that the surface charge plays the crucial role in the bacterial adhesion on uncoated and coated PVC catheter surfaces.