The present invention relates to 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 characterized in that the said composition further comprises one or more of (b) aliphatic amines selected from a group comprising tertiary amines, secondary amines and primary amines. In one embodiment, the present invention also relates to method of use of 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.