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We report time-resolved and angle-resolved photoemission spectroscopy on SnSe and Sn1−xNaxSe (x = 0.015) which currently attract great interest due to their extremely high thermoelectric performance. The valence band of SnSe exhibits upward energy shift of ∼0.2 eV due to the photoexcitation while that of Sn1−xNaxSe does not show appreciable energy shift. As for SnSe, within 50 fs after the pump pulse arrival, the conduction band bottom is observed just above the valence band maximum near the Z point while the conduction band is located around 0.5 eV above the Fermi level near the Γ point. This suggests that the band gap is collapsed by the photoexcitation due to downward and non-rigid band shift of the conduction band. At 80 fs after the pump pulse arrival, the band gap is recovered, and the conduction electrons are almost depleted with some residual populations around minimum points of the conduction bands.