The interest in cluster chemistry lies not only in the development of new types of geometric structures but also in the higher-level connectivity and assembly of clusters at the supramolecular level. Here, we report a novel windmill-like Al10 cluster and consider this geometrically unique cluster as an anionic node assembled together with different cationic guests such as imidazolium and guanidinium. These guests with different hydrogen-bond angles can help to obtain a series of diverse hydrogen-bonding networks and then manipulate the stacking mode of hosts and guests. Furthermore, we realized a supramolecular approach to fine-tune the optical limiting properties of the cluster. This work not only enriches the host-guest chemistry of ionic windmill-like clusters but also opens up more possibilities for aluminum oxo cluster-based hydrogen-bonded frameworks.