In this work, we have demonstrated a different effect on Fe1+σTe0.5Se0.5 and β-FeSe by changing the quenching temperature. Tc is clearly reduced in Fe1+σTe0.5Se0.5 after increasing the quenching temperature from 300 °C to 500 °C, while that of β-FeSe is almost unchanged. Structure refinement indicates that after quenched at 500 °C, FeTe4 tetrahedron exhibits an expansion with the stretched Fe-Te bond, together with the increased amount of interstitial iron. These particular changes on structure are believed to be responsible for the suppression of superconductivity in Fe1+σTe0.5Se0.5.