The adsorption of N2O on Cu(100) has been studied by using scanning tunneling microscopy (STM). In the first molecular layer N2O forms a densely packed c(3 × 2) structure, in which the molecules occupy two different adsorption sites. The bonding strength of this layer is found to be very weak as revealed by a low desorption temperature and the formation of misalignments and defects. Density functional theory (DFT) finds a stable c(3 × 2) structure in which the molecules are considerably bent due to charge transfer. In model calculations for a 2 × 2 hollow phase we show that in order to reach the chemisorbed, bent configuration, the molecules have to pass an activation barrier. In the experimentally accessible range, this is apparently not possible and the molecules remain in a stable physisorbed state.