In our previous work, highly (00.1)-textured, photoactive WSe 2 films have been prepared by a sequential amorphous solid-liquid-crystalline solid process (aSLcS). The pristine WSe 2 films exhibit a high photoactivity in the bulk, derived from time resolved microwave conductivity (TRMC) measurements, but only a very low photocatalytical activity upon illumination in an electrolyte. This was explained by a low charge carrier transfer rate via the (00.1) van der Waals planes to the SEI. Even, when evaporating a thin Pt film as a HER catalyst homogeneously onto the WSe 2 van der Waals planes, no significant photocurrent can be observed. However, when depositing photochemically Pt nanoislands preferentially at the crystallite edges, the transfer from the edge sites of WSe 2 crystallites to the semiconductor-electrolyte interface can be significantly improved. This clearly shows that Pt acts as a HER catalyst only at the edges of (00.1)oriented WSe 2 crystallites.