The possibility of utilizing semiconductor thin films based electronic nose for the detection of phosphine in post-fumigated grain for the control of quality of wheat products has been investigated. Undoped, Rh-, Ni-, and Os-doped SnO2 thin films have been deposited by the sol–gel spin-coating method and their gas-sensing properties towards different concentrations of PH3 have been analyzed. The sensors were exposed to the volatiles of uncontaminated and differently fumigated cereal samples. The data coming from the response of the sensors have been elaborated by PCA method. The obtained results showed a very good capability of the array to discriminate different contaminated samples.