Dihydroxy derivative of vanillin-based diaminotriazole core monomer (DTV) has been synthesized using sustainable vanillin (V) and 3,5-diamino-1,2,4-triazole (DT) under appropriate experimental conditions and characterized with a view to develop Schiff base core nitrogen-rich benzoxazines capable of exhibiting excellent optical and anti-microbial properties. The monomer DTV has been subsequently converted into benzoxazines separately using six structurally varied amino compounds, viz. aniline (a), 1-(−2-aminoethyl)piperazine (aep), furfurylamine (ffa), 4-H-1,2,4-triazoal-4-amine (ta), 3-aminopyrazol (apy) and 1-(3-aminopropyl)imidazole (api) with paraformaldehyde through Mannich condensation. The corresponding Schiff base based benzoxazines, viz. DTV-a, DTV-aep, DTV-ffa, DTV-ta, DTV-apy and DTV-api were synthesized and characterized for their molecular structure, thermal stability, optical, hydrophobic and anti-microbial properties using different analytical techniques and methods. Data obtained from different analyses for DTV based benzoxazines can be used for wide range of industrial and engineering applications.