An efficient nitration of silyl allenes with nitrogen dioxide radical, generated from NaNO2 and AcOH, to form α-nitro-α,β-unsaturated silyl oximes has been developed. A similar nitration could be achieved by using Fe(NO3)3·9H2O and FeCl3·6H2O, but different from the regioselective oxime formation, two regioisomeric chloride-trapped products were isolated with varying ratios depending on the steric bulk of the silyl group. A novel ring-closure reaction of α-nitro-α,β-unsaturated silyl oximes upon treating with TBAF to form isooxazolidinone derivatives was also developed.