Dye photodegradation is an important research topic, and great efforts have been made to target the photocatalysts with highly efficient and selective performance. Reported here are two layered anion chalcogenide frameworks with semiconducting properties combined with highly open interlayer spaces, which are used as efficient photocatalysts to show excellent size and charge selectivity towards organic dye molecules. In addition, the organic templates inside the chalcogenide frameworks are exchanged via an ion-exchange process, and the resulting host frameworks with much looser internal spaces play significant roles in improving the photocatalytic activity.