The effect of additives on metal/oxide interfaces is explored in situ and in real time on evaporated films by a combination of surface science techniques, among which a very flexible optical method shows a unique ability to scrutinize the growth and wetting properties of supported clusters that involve several elements. The study focuses on Cr at the Zn/α-Al2O3(0001) interface at 300 K. A particular interest of the present interface is that Zn does not stick at all on bare alumina. The sticking and morphology of both Cr and Zn films during their growth are analyzed from sub-monolayer to multilayer thicknesses. After an initial oxidation reaction with residual OH groups, shown to be detrimental to Zn adhesion, Cr growth proceeds through the formation of high aspect ratio particles that percolate around an average thickness of 10 Å. With regard to Zn growth on a Cr deposit, two very distinct stages can be distinguished. In the sub-monolayer thickness range, Cr forms a seed layer that drastically increases the Zn sticking coefficient from 0 to nearly 1 due to a diffusion length of physisorbed Zn adatoms before desorption larger than Cr island separation; Zn clusters are anchored on the Cr seeds that they encapsulate, but their wetting behavior is dictated by the interaction with alumina. In a second stage, as soon as the Cr film percolates, it forms an adhesion layer on which Zn grows in a nearly two-dimensional mode. In all cases, Cr films are stable upon annealing. On Cr-covered alumina, the Zn desorption energy is enhanced as compared to bare surfaces, which, in line with atomistic simulations, is assigned to the formation of more favorable Cr–Al2O3 and Cr–Zn than Zn–Al2O3 bonds. Generally speaking, the ability demonstrated herein of small amounts of additives to dramatically increase the adhesion of films is of great practical interest. It shows that noncontinuous and partially oxidized films of additives, closer to realistic cases of application, can strongly enhance the sticking of films. Also, anchoring a functional film by discrete predeposited seeds can keep its properties intact.