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              <p>Surface fluorination improves the photocatalytic activity of TiO&lt;sub&gt;2&lt;/sub&gt;, and the influences of various features of fluorinated TiO&lt;sub&gt;2&lt;/sub&gt; (TiO&lt;sub&gt;2&lt;/sub&gt;–F) have often been discussed in the literature. The present paper addresses the changes induced by surface fluorination on the morphological, structural, surface, and electronic features of TiO&lt;sub&gt;2&lt;/sub&gt;. In particular, X-ray diffraction, specific surface area analysis, and transmission and scanning electron microscopy give evidence that surface fluorination does not affect the structural properties and the morphology of TiO&lt;sub&gt;2&lt;/sub&gt; nanoparticles. In contrast, fluorination induces changes of surface and electronic properties. Chemical and thermogravimetric analyses show that surface fluorination can reach up to 50% of original Ti–OH surface sites. The surface charge of TiO&lt;sub&gt;2&lt;/sub&gt; turns more negative upon fluorination, as shown by a shift of the point of zero charge toward lower pH. Electronic properties are deeply characterized by combining diffuse reflectance, X-ray, and UV photoelectron spectroscopies, as well as time-resolved fluorescence spectroscopy, and photoelectrochemical measurements. Results show the presence of intra-band-gap energy states induced by the local interaction of chemisorbed fluorine atoms. Such energy levels are close to the valence band. The unique surface and electronic properties of TiO&lt;sub&gt;2&lt;/sub&gt;–F make it a promising material for the photocatalytic degradation of poorly soluble emerging pollutants such as 1-methylnaphtalene. In particular, TiO&lt;sub&gt;2&lt;/sub&gt;–F demonstrates faster degradation kinetics with respect to both the pristine material and TiO&lt;sub&gt;2&lt;/sub&gt; P25 used as a benchmark standard.</p>
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