In the medical field, polydioxanone (PDO) has increasingly attracted scientific interests in both fundamental research and applications for synthesizing sutures due to its safety, biodegradability, and mechanical strength. Chemical pathways of the aforementioned architecture have already been proven via a plethora of multidisciplinary researches, however, the physical nature of PDO filaments by each stage of the synthetic condition has yet been solely observed in detail. The scope of the present study tracks a couple of pre- and post-fiberation to tailor the success in tunable physical strength with the variance of purification time and the dosage of a catalyst. We first fabricated PDO filaments using lauryl alcohol (C12H26O) and stannous octoate (C16H30O4Sn) as an initiator and a catalyst, respectively. PDO-3-30 with 3 h of vacuum purification and 30 ppm dosage of a catalyst led to unfavorable thermal properties and degradability but an increase in physical properties including tensile, flexural, and Izod impact strengths. From thermal and physical profiles, it was confirmed that the amount of a catalyst is a major driving factor of polymerization while the degree of purification could be an additive aid for more sensitive control of the physical nature of PDO filaments.