The present invention relates to amine based additive composition for controlling and inhibition of polymerization of aromatic vinyl monomers including styrene comprising (a) one or more of nitroxide (i.e. nitroxyl) compounds; and (b) one or more of aromatic nitro compounds, characterized in that the said composition further comprises one or more of (c) amines, wherein said amine is selected from a group comprising (i) hydroxyl alkyl tertiary amines, (ii) tertiary alkyl amines, (iii) hydroxyl alkyl primary amine; and (iv) mixture thereof. In one embodiment, the present invention also relates to method of using presently provided composition. In another embodiment, the present invention also relates to method of controlling and inhibiting polymerization of aromatic vinyl monomers including styrene by employing presently provided composition. In still another embodiment, the present invention also relates to method of preparation of presently provided composition.