Xe adsorption on the (100) surface of the complex alloy Al 13 Co 4 has been carried out using lowenergy electron diffraction (LEED) and grand canonical Monte Carlo (GCMC) simulations. This surface is an approximant to the 10-fold surface of decagonal Al-Ni-Co, on which Xe adsorption had been studied earlier. The adsorption behavior on the periodic surface is largely similar to that on the quasicrystal (layer-by-layer growth, hexagonal ordering near the onset of the 2 nd-layer adsorption) but also has some differences, such as the complete lack of registry of the Xe layer with the substrate structure in the hexagonal phase, and a high sensitivity of the Xe epitaxial direction to trace impurities. An ordering transition between the low-density and highdensity monolayer regimes was observed in the simulations, which involves a uniaxial compression of the monolayer film. Al 13 Co 4 has 102 atoms per unit cell, and its orthorhombic lattice parameters are a = 8.158 Å, b = 12.342 Å and c = 14.452 Å as determined from x-ray diffraction 23. Its structure along the [100] direction can be described as the stacking of two types of layers, flat (F) having 17 Al and 8 Co atoms, and puckered (P), having 22 Al and 4 Co atoms. There are two types of each plane,