Despite the remarkable optical properties of rare-earth ion materials, their applications as light sources and in quantum technologies are often hindered by their long lifetimes and weak emission.Leveraging the natural compatibility of rare-earth ion molecular complexes with photonic structures, here we modify their photoluminescence properties by coupling them to a flexible open Fabry-Pérot cavity. The full in situ tunability of the Fabry-Pérot cavity allows fine control over its cavity modes and the achievement of resonant coupling between the rare-earth ion emission and the cavity modes. This configuration allows us to achieve a maximum photoluminescence enhancement factor of 30 and accelerate the decay rate up to two orders of magnitude. Our pumppower dependent spectroscopic studies of the emitter-cavity system suggests that the cavitymodified emission is primarily caused by amplified spontaneous emission. These results suggest that integrating rare-earth ion molecular complexes with photonic structures could be a viable approach for the effective tuning of their optical properties. This natural compatibility, together with their versatile molecular structures and the resultant electronic states, renders rare-earth ion molecular complexes a potential alternative material platform for lighting and quantum applications.