In the present work, pyrazolidine bisphenol (PYBP)-based superhydrophobic/superoleophilic benzoxazine (PBz) matrices were synthesized and described in comparison with bisphenol F benzoxazines. The preliminary in vitro toxicity assay reveals the nontoxic nature of PYBP. Data obtained from thermal and surface studies indicate that the prepared PYBP-based PBzs have enhanced thermal stability than those of bisphenol F benzoxazines. Further, the prepared PYBP-based PBz-coated cotton fabric displayed superior water contact angle (WCA = 154.7°) and sliding contact angle (θ = 9°). Observations from SEM images suggest that the inherent superhydrophobic nature was due to the formation of rough surfaces. Furthermore, oil-water separation was successfully ascertained from the appropriate experimental conditions using the PYBP-coated fabric. The separation efficiency and flux are found to be greater than 90% after 10 cycles. Thus, the PYBP-based superhydrophobic/superoleophilic polybenzoxazines (PBzs) have been synthesized and characterized to assess their suitability for water-repellent and oil-water separation applications.