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Two-dimensional metal-organic porous networks (2D-MOPNs) are highly orderedquantum boxes for exploring surface confinements. In this context, the electronconfinement from occupied Shockley-type surface states (SS) has been vigorouslystudied in 2D-MOPNs. In contrast, the confinement of excited surface states,such as image potential states (IPSs), remains elusive. In this work, we applytwo-photon photoemission to investigate the confinement exemplarily for thefirst image state in a Cu-coordinated T4PT porous network (Cu-T4PT). Due to thelateral potential confinement in the Cu-T4PT, periodic replicas of the IPS aswell as the SS are present in a momentum map. Surprisingly, the first IPStransforms into a nearly flat band with a substantial increase of the effectivemass (> 150 %), while the band dispersion of the SS is almost unchanged. Thegiant confinement effect of the excited electrons can be attributed to thewavefunction location of the first IPS perpendicular to the surface, where themajority probability density mainly resides at the same height as repulsivepotentials formed by the Cu-T4PT network. This coincidence leads to a moreeffective scattering barrier to the IPS electrons, which is not observed in theSS. Our findings demonstrate that the vertical potential landscape in a porousarchitecture also plays a crucial role in surface electron confinement.

Giant confinement of excited surface electrons in a two-dimensional metal-organic porous network