A scanning tunneling microscopy (STM) study, combined with density functional theory (DFT) calculations and thermal desorption spectroscopy (TDS) data, on the growth and structure of Zn on a Pd(111) surface is presented. The STM results demonstrate that PdZn(111) surface alloy bilayer islands with a p(2 × 1) structure already form during the room temperature deposition of submonolayer amounts of Zn on Pd(111). DFT calculations predict that the PdZn bilayers are energetically more stable than single PdZn layers and establish their structural parameters. The TDS data show that Zn desorbs below 600 K in a multiple-peak desorption structure with fractional order desorption kinetics of the individual components, which is due to multilayer Zn desorption. The experimentally derived adsorption energies of the low temperature desorption peaks are reproduced in the DFT calculations. At temperatures above 750 K, Zn desorbs from the PdZn alloy, and the desorption kinetics is a mixture of a first-order and a diffusion-limited desorption process.