Polycrystalline ZnO is a material often used in heterogeneous catalysis. Its properties can be altered by the addition of dopants. We used gaseous fluorine (F2(g)) as direct way to incorporate fluoride in ZnO as anionic dopants. Here, the consequences of this treatment on the structural and electronic properties, as well as on the acidic/basic sites of the surface, are investigated. It is shown that the amount of F incorporation into the structure can be controlled by the synthesis parameters (t, T, p). While the surface of ZnO was altered as shown by, e.g., IR spectroscopy, XPS, and STEM/EDX measurements, the F2 treatment also influenced the electronic properties (optical band gap, conductivity) of ZnO. Furthermore, the Lewis acidity/basicity of the surface was affected which is evidenced by using, e.g., different probe molecules (CO2, NH3). In situ investigations of the fluorination process offer valuable insights on the fluorination process itself.