Mechanochemistry is well-established in the solid-phase synthesis of inorganic materials but has rarely been employed for molecular syntheses. In recent years, there has been nascent interest in 'greener' synthetic methods with less solvent, higher yields, and shorter reaction times being especially appealing to the fine chemicals and inorganic catalyst industries. Herein, we demonstrate that main-group indium(iii) complexes featuring bis(imino)acenaphthene (BIAN) ligands are readily accessible through a mechanochemical milling approach. The synthetic methodology reported herein not only bypasses the use of large solvent quantities and transition metal reagents for ligand synthesis, but also reduces reaction times dramatically. These new main-group complexes exhibit the potential to be reduced to indium(i) compounds, which may be employed as photosensitizers in organic catalyses and functional materials. © 2016 The Royal Society of Chemistry.