The objective of the present work is to synthesize three different types of cardanol based benzoxazines such as cardanol-{1,4-bis(4-aminophenoxy)ethane}benzoxazine (CBAE2Bz), cardanol-{1,4-bis(4-aminophenoxy)butane} benzoxazine (CBAE4Bz) and cardanol-{1,4-bis(4-aminophenoxy)octane}benzoxazine (CBAE8Bz) by varying aliphatic ether link chain length through solventless method. The benzoxazines obtained with varying chain length were converted in to three different types of composites using paraphenylenediamine (PPDA) functionalized gaphene oxide (f-GO) as nano-reinforcement with varying weight percentage and were characterized by different analytical techniques. The molecular structure of the monomers was confirmed from Fourier transform infrared (FTIR) spectroscopy, 1HNMR, 13C NMR and MALDI mass. Data obtained from thermal studies infer that the prepared composites possess good thermal stability and enhanced values of Tg with respect to weight percent of functionalized graphene oxide content. However, the values of thermal stability, Tg, dielectric constant and dielectric loss were marginally decreased with respect to increase in length of the spacer aliphatic chain. The SEM and TEM studies confirm the homogeneous dispersion and single layer thickness of graphene sheet, respectively. The feasibility of usage of f-GO/PCAE2Bz composite in both gram positive bacteria (Bacillus subtilis, Staphylococcus aureus) and gram negative bacteria (Pseudomonas aeruginosa, Escherichia coli) environments were checked and the results obtained were discussed. Further, third-order NLO properties of open and closed aperture Z–scan results conclude that GO doped bio-resource based composites exhibit saturable absorption and self-defocusing type optical non-linearity. The third-order NLO susceptibility (χ3) of GO doped bio-resource based composites are increased with respect to quantity of reinforcement of GO to bio-based polymer. The maximum value of 1.03X 10−4 esu was observed and this nonlinearity is thermal in nature. Thus, the prepared composites may find wide range of applications in diverse surrounding conditions