Unsymmetric Organotin(IV) compounds of general formula R4-nSnR'(n) have been synthesized by the reaction of corresponding organotin(IV) chlorides with n-hexyl magnesium bromide prepared in dry ether in situ, where R = CH3, n-C4H9, C6H5, C6H5CH2 and W = n-C6H13. The reactions were carried out in dry toluene, refluxed for 6 h and the final products were purified through vacuum distillation. These compounds were characterized by multinuclear NMR (H-1, C-13, Sn-119), IR spectroscopy and mass spectrometry to predict their structures. All spectroscopic results support the four-coordination and tetrahedral geometry of the compounds.