The dielectric confinement effect plays an essential role in optoelectronic devices. Existing studies on the relationship between the dielectric confinement and the photoelectric properties are inadequate. Herein, three organic spacers with different dielectric constants are employed to tune the exciton dynamics of quasi-two-dimensional (quasi-2D) Ruddlesden–Popper perovskite films. Femtosecond transient absorption spectroscopy reveals that the small dielectric constant ligand enables a weak dynamic disorder and a large modulation depth of the coherent phonons, resulting in a more complete energy transfer and the inhibition of a trap-mediated nonradiative recombination. Additionally, the increase in the bulk-ligand dielectric constant reduces the corresponding exciton binding energy and then suppresses the Auger recombination, which is beneficial for high-luminance light-emitting diodes. This work emphasizes the importance of dielectric confinement for regulating the exciton dynamics of layered perovskites.