Valence molecular orbitals play a crucial role in chemical reactions. Here, we reveal that an intense laser field deforms an inner valence orbital (10a′) in the ethanol molecule. We measure the recoil-frame photoelectron angular distribution (RFPAD), which corresponds to the orientation dependence of the ionization probability of the orbital, using photoelectron-photoion coincidence momentum imaging with a circularly polarized laser pulse. Ab initio simulations show that the orbital deformation

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... depends strongly on the laser field direction and that the measured RFPAD cannot be reproduced without taking the orbital deformation into account. Our findings suggest that the laser-induced orbital deformation occurs before electron emission on a suboptical cycle time scale.