In the present work, hybridized bio-based benzoxazines were developed with a green strategy for shape memory applications. Herein, two bio-based materials of cardanol and guaiacol were utilized to synthesize bio-based benzoxazine monomers of cardanol-Jeffamine D230 (CJ) and bis-guaiacol-furfurylamine (BGF) by using a solvent-free method. Different weight percentage ratios (wt %) of BGF and CJ benzoxazines were hybridized (BGF-CJ – 100–0, 80–20, 60–40, 40–60 and 0–100) and studied their thermal stimulus responsive properties. The structure of synthesized benzoxazine was analyzed using 1H nuclear magnetic resonance (NMR) spectroscopy and Fourier transform infra-red (FTIR) spectroscopy. The thermal properties of polybenzoxazines were analyzed by thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC). Among the co-polymers, P(BGF20-CJ80) shows the lower value of glass transition temperature with the highest degradation temperature. Similarly, the co-polymer of P(BGF60-CJ40) possess excellent shape memory properties and for consecutive analysis, the shape fixity ratio is 95 − 96 % for BGF60-CJ40, and its shape recovery ratio is 98–100 %. The principle behind this excellent performance results were related to the synergistic effects of rigid cross-linked oxazine rings and long aliphatic chain present in cardanol-Jeffamine D230 benzoxazine. The present research work is mainly focused on the utilization of bio-based raw materials, and the replacement of fossil-based bisphenol-A, with an objective of alleviation of environmental problems.