The instability of halide perovskites toward moisture is one of the main challenges in the field that needs to be overcome to successfully integrate these materials in commercially viable technologies. One of the most popular ways to ensure device stability is to form 2D/3D interfaces by using bulky organic molecules on top of the 3D perovskite thin film. Despite its promise, it is unclear whether this approach is able to avoid 3D bulk degradation under accelerated aging conditions, i.e., thermal stress and light soaking. In this regard, it is crucial to know whether the interface is structurally and electronically stable or not. In this work, we use the bulky phenethylammonium cation (PEA+) to form 2D layers on top of 3D single- and triple-cation halide perovskite films. The dynamical change of the 2D/3D interface is monitored under thermal stress and light soaking by in situ photoluminescence. We find that under pristine conditions the large organic cation diffuses only in 3D perovskite thin films of poor structural stability, i.e., single-cation MAPbI3. The same diffusion and a dynamical change of the crystalline structure of the 2D/3D interface are observed even on high-quality 3D films, i.e., triple-cation MAFACsPbI3, upon thermal stress at 85 °C and light soaking. Importantly,