Crystal and molecular structure and the thermal properties of (N,N-dibencyl)-4-nitrophenylsulfenamide, (C6H5CH2)2 NSC6H4-4-NO2, is herein presented. The structure is a divalent sulfur compound that crystallized in the monoclinic system, space group P2(1)/c with a=9.274(2), b=6.013(1), c=32.147(9) Å, b=95.55(2) and Dx=1.305 g cm-3 with Z=4. The plane C-S-N form a dihedral angle of 77.4(3) with the plane C19-N1-C20, and it represent a notable difference with other sulfenamides described in the literature. The thermogravimetric analysis reveal a decomposition of the product in two steps and another event, probably, associated to a endothermic phase transition