Parylene is an important class of polymer thin film that has wide-ranging applications due to its well-recognized properties, such as low-dielectric constant, biocompatibility, and exceptional barrier properties. Here, we studied the deposition of parylene nanofibers by template-based and template-free methods, which combine both vapor deposition polymerization and oblique angle deposition. A comparative study of two approaches based on surface characterization techniques is presented. These nanofibers, deposited by both approaches, have potential applications in catalysis, biodetection, and biomedical coatings.