In this study, the blends of bio-based polybenzoxazine (V-fa type) and poly(ethylene glycol) (PEG) with PEG contents from 50 to 95 wt% and different molecular weights were developed to improve the flexibility of thermosetting polymers. Of these blends, PEG 8k at 80 wt%, which exhibited the best processability, was selected for further development via compositing with carbon black (CB) from 0 to 20 phr. Differential Scanning Calorimetry (DSC) analysis revealed that the melting temperature (T_m) increased from 70 to 83 °C and glass transition temperatures (T_g) increased from –53 to –48 °C at 20 phr. Thermogravimetric Analysis (TGA) demonstrated high thermal stability, with T_dmax (for all CB contents) presented at ca. 416 °C. Moreover, char yield was increased from 10% (without CB) to 28% (20 phr), reflecting improved decomposition resistance. Mechanical properties demonstrated that CB significantly reinforced the composites. The flexural modulus and flexural strength were increased from 117.18 MPa (without CB) to 456 MPa (10 phr) and from 2.42 MPa (without CB) to 3.94 MPa (2.5 phr), respectively. The SEM images confirmed uniform morphology and good filler dispersion. Conclusively, the composites of 8k PEG 80 wt% filled with 2.5 phr of CB provided an optimal balance of mechanical and thermal stability and engineering polymer applications.