Organic materials can tune the optical properties in layered (2D) hybrid perovskites, although their impact on photophysics is often overlooked. Here, we use transient absorption spectroscopy to probe the Dion–Jacobson (DJ) and Ruddlesden–Popper (RP) 2D perovskite phases. We show the formation of charge transfer excitons in DJ phases, resulting in a photoinduced Stark effect which is shown to be dependent on the spacer size. By using electroabsorption spectroscopy, we quantify the strength of the photoinduced electric field, while temperature-dependent measurements demonstrate new features in the transient spectra of RP phases at low temperatures resulting from the quantum-confined Stark effect. This study reveals the impact of spacer size and perovskite phase configuration on charge transfer excitons in 2D perovskites of interest to their advanced material design.