Stepped spin crossover (SCO) complexes with three or more spin states have promising applications in high-order data storage, multi-switches and multi-sensors. Further synergy with other functionalities, such as luminescence and dielectric properties, will provide a good chance to develop novel multifunctional SCO materials. Here, a bent pillar ligand and luminescent pyrene guest are integrated into a three-dimensional (3D) Hofmann-type metal–organic framework (MOF) [Fe(dpoda){Au(CN)₂}₂]·pyrene (dpoda = 2,5-di-(pyridyl)-1,3,4-oxadiazole). The magnetic data show an incomplete and two-step SCO behavior with the sequence of 1 ↔ 1/2 ↔ 1/4. The rare bi-directional light-induced excited spin-state trapping (LIESST) effect and light-induced stepped thermal relaxation after LIESST are observed. The pyrene guests interact with dpoda ligands via offset face-to-face π⋯π interactions to form intermolecular exciplex emissions. The competition between thermal quenching and stepped SCO properties results in a complicated and stepped exciplex fluorescence. Moreover, the stepped dielectric property with higher dielectric permittivity at lower temperature may be related to the more frustrated octahedral distortion parameters in the intermediate spin states. Hence, a 3D Hofmann-type MOF with bent pillar ligands and fluorescent guests illustrates an effective way for the development of multifunctional switching materials.