In this work, we explored a post-synthetic modification of the well-known graphitic carbon nitride (g-CN) by means of an “amorphization” treatment and evaluate the resulting change in photocatalytic activity towards the synthesis of valuable perfluoroalkyl derivatives. The as-prepared “super-amorphous” CN (SACN) exhibits a significant increase of the photocatalytic activity (up to a six-fold enhancement with the optimum structure with respect to g-CN), which originates from the lower degree of crystallinity of the CN and its reduced bandgap. The SACN photocatalysts display versatility and good tolerance towards functional group variations of the reagents, emerging as a potential new benchmark CN structure for heterogeneous organic photocatalysis.