Controlled synthesis of rare-earth metal-organic frameworks (RE-MOFs) is of great significance to match their emerging multifunctional luminescence applications. Herein, we propose a green and general solvent-free synthetic strategy for the adjustment of morphology and dimension of various RE-MOFs (RE = Eu, Tb, Er, Dy, Y, Tm) by using a tetraethylammonium bromide-assisted thermal-heating method. These self-assembled RE-MOF materials possess controllable morphologies and hierarchical structures while retaining the structural topology of MIL-78, proving that the strategy is a feasible and effective way in opening up large-scale synthesis of RE-MOFs. It is further found that the tetraethylammonium could be carbonized into carbon dots and encapsulated in Eu/Tb-MIL-78 to enhance the fluorescence emission intensities significantly, making the hierarchical Eu/Tb-MIL-78 MOF materials good candidates for the latent fingerprints recognition application. This work provides a novel strategy for effectively controlling the morphology and dimension of RE-MOFs materials with enhanced photoluminescence and has great potential in their scaling-up syntheses and exploring the new luminescence applications.