Luminescent thin films containing Eu3+ β-diketonate complexes fabricated by the Langmuir-Schaefer (LS) technique find several applications such as in light-converting molecular devices or in solid-state lighting.[1] However, the main challenge concerning their fabrication lies in the deposition control and homogeneity of the films since the complexes usually display high hydrophobicity.[2] To overcome this issue, in this study, we have investigated the fabrication of LS films based on [Q][Eu(dbm)4)] complexes (Hdbm = 1,3-diphenyl-1,3-propanedione, Q1 = C26H56N+, Q2 = C19H42N+, or Q3 = C17H38N+)[3],[4] in order to use amphiphilic counter-ions to organize the luminescent anionic complex on the subtract. To fabricate the LS films, a basin was used with ultrapure water in the liquid subphase at 25 ºC. For the fabrication of each film, a certain amount of the complex in chloroform was spread out on the aqueous subphase. After the solvent evaporation, it got started the movable barrier compression at constant velocity of 10 mm.min-1. Along with the compression process, surface pressure versus mean molecular area (π-A) isotherms were obtained. The complex was transferred to the hydrophilic glass substrate in the horizontal position by using the deposition mode called Z-type, under surface pressure of 20 mN.m-1. For all films, 11 layers were deposited onto the substrates, monitored by UV-VIS absorption spectra. The amphiphilic counter-ions play an important role in the film fabrication by increasing the surface homogeneity and deposition quality as the carbonic chain increases, especially for the [Q1][Eu(dbm)4)] film, which showed a root mean square surface roughness of 37.8 nm recorded by atomic force microscopy. All films displayed the characteristic Eu3+ red-light emission under excitation at 367 nm, and the best 5D0 state quantum efficiency of Eu3+ was achieved for the [Q1][Eu(dbm)4)] film (27.5 %), confirming that the counter-ion also influences the luminescent properties of the films due to changes in the complex conformation.