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 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 prior to electron emission on a sub-optical-cycle time scale.