Double perovskites are promising candidates for less toxic and highly stable metal halide perovskites, but their optoelectronic performances still lag behind those of the lead halide counterpart, due to the indirect nature of the bandgap and the strong electron–phonon coupling. Reducing the dimensionality of Cs2AgBiBr6 down to a 2D layered form is strategic in order to tune the band gap from indirect to direct and provides new insights into the structure–property relationships of double perovskites. Herein, we report on a series of monolayer 2D hybrid double perovskites of formula (RA)4AgBiBr8, where RA represents different primary ammonium large cations with alkyl- and aryl-based functionalities. An in-depth experimental characterization of structure, film morphology, and optical properties of these perovskites is carried out. Interestingly, the variation of the ammonium cation and the interplanar distance between adjacent inorganic monolayers has peculiar effects on the film-forming ability and light emission properties of the perovskites. Experiments have been combined with DFT calculations in order to understand the possible origin of the different emissive features. Our study provides a toolbox for future rational developments of 2D double perovskites, with the aim of narrowing the gap with lead halide perovskite optoelectronic properties.