The syntheses and structural elucidation of dimeric [Sn(OCyHex)2] (1), its corresponding (cyclohexoxy)alkalistannates(II) [{M(OCyHex)3Sn}2] (M=Li (2), Na (3), K (4)), and of the first heteroleptic heterotermetallic Li/In/Snhaloalkoxide clusters [X2In{LiSn2(OCyHex)6}] (X=Br (5), Cl (6)) with a double seco-norcubane core are reported. They represent suitable precursors for new amorphous indium tin oxide (ITO) materials as transparent conducting oxides with drastically reduced concentrations of expensive indium, while maintaining their high electrical performance. In fact, compounds 5 and 6 were successfully degraded under dry synthetic air at relatively low temperature, resulting in new semiconducting tin-rich ITOs homogeneously dispersed in a tin oxide/lithium oxide matrix. The obtained particles were investigated and characterised by different analytical techniques, such as powder XRD, IR spectroscopy, SEM, TEM and energy-dispersive X-ray spectroscopy (EDX). The analytical data confirm that the final materials consist of tin-containing indium oxide embedded in an amorphous tin oxide matrix. The typical broadening and shift of the observed indium oxide reflections to higher 2? values in the powder XRD pattern clearly indicated that tin centres were successfully incorporated into the In2O3 lattice and partially occupied In3+ sites. Investigations by EDX mapping proved that Sn was homogeneously distributed in the final materials. Thin-film field-effect transistors (FETs) were fabricated by spin-coating of silicon wafers with solutions of 5 in toluene and subsequent calcination under dry air (25700 degrees C). The FETs prepared with precursor 5 exhibited excellent performances, as shown by a charge-carrier mobility of 6.36 x 10(-1) cm2?V-1?s (calcination at 250 degrees C) and an on/off current ratio of 106.