The use of large amounts of deleterious solvents in the synthesis of metal–organic frameworks (MOFs) is one of the important factors limiting their application in industry. Herein, we present a detailed study of the synthesis of UiO-66, which was conducted with hydrobromic (HBr) acid as a modulator for the first time, at a high concentration of precursor solution (ZrCl₄ and H₂BDC, both 0.2 mol L⁻¹). Powder crystals with atypical cuboctahedron structure were obtained which indicated that the HBr acid modulator played roles by competitive coordination and deprotonation modulation, thereby controlling the processes of nucleation and crystal growth. The properties of the obtained materials were systematically characterized and compared with those of materials synthesized with hydrofluoric (HF) acid and hydrochloric (HCl) acid modulators. Despite the high concentration of defectivity, the UiO-66 material synthesized with the HBr acid additive has the characteristics of larger specific surface area, excellent thermal stability and higher porosity in the structure. Besides that, the present protocol has the advantages of high reaction mass efficiency (RME), and feasibility of scalable synthesis, providing a facile and sustainable route to diverse Zr-based MOFs.