Full wave profiles are used to determine the Hugoniot elastic limit and the spall strength of armco iron samples with an as-received structure and the samples recovered after preliminary loading by plane shock waves with an amplitude of 8, 17, and 35 GPa. The measurements are performed at a shock compression pressure below and above the polymorphic a–e transition pressure. Metallographic analysis of the structure of armco iron shows that a developed twinned structure forms inside grains in the samples subjected to preliminary compression and recovered and that the twin concentration and size increase with the shock compression pressure. The spall strength of armco iron under shock loading below the phase transition pressure increases by approximately 10% due to its preliminary deformation twinning at the maximum shock compression pressure. The spallation of samples with various structures at a shock compression pressure above the phase transition proceeds at almost the same tensile stresses. The polymorphic transition in armco iron weakly affects its strength characteristics.