Six biofilm carriers with different polymer were studied in fixed-film systems under anoxic conditions. Different media of polymers influence wastewater treatment performance. The aim of this study was to investigate different polymeric materials, polyethylene terephthalate (PET), polyvinyl chloride (PVC), polypropylene (PP), high-density polyethylene (HDPE), and polymethyl methacrylate (acrylic), that affect bacterial attachment and biofilm formation in biofilm-based wastewater treatment technologies. Water contact angle (WCA) measurement was employed to analyze the role of wetting (hydrophilic/hydrophobic) of polymeric material surfaces in the initial phase of bacterial attachment. The increase of biofilm formation during the observation was determined by gravimetric (total attached solid) and microscopic (SEM and CLSM) analysis. The results showed the value for WCA of PET < HDPE < PVC < PP < acrylic, which indicated that a higher hydrophilicity surface leads to a higher total attached solid (TAS), biofilm formation rate, and biofilm thickness on the surface of media. The hydrophilic material (i.e., PET and HDPE) demonstrated wastewater treatment performance better than slightly hydrophilic material (i.e., PVC, PP, and acrylic) under a steady-state period (over an 80-day operation). The data showed a positive correlation between hydrophilic material and COD, NH4+-N, and TP removal. Hydrophilic material was beneficial for a fast start-up and stable biofilm formation of a fixed-bed biofilm reactor. PET media showed feasible polymer types compared to HDPE, PVC, and PP; thus, it can be used as an alternative biofilm carrier media in a larger-scale application. The findings of this study highlighted the polymeric material type has a significant effect on the performance of fixed-bed wastewater treatment.