Three novel fluorescent fluoro-silicon(IV) complexes of the type [SiF3(L)] (HL = Schiff base) were synthesized, and their properties were investigated: one of the complexes [SiF3(L1)] (1; Phi(F) = 0.96; HL1 = 2-hydroxy-1-naphthylmethylene-8-aminoquinoline) shows an extremely high fluorescence quantum yield, and other complexes [SiF3(L2)] (2; Phi(F) = 0.11; HL2 = 3,5-dichlorosalicylidene-8-aminoquinoline) and [SiF3(L3)] (3; Phi(F) -= 0.01; HL3 = 3,5-dibromosalicylidene-8-aminoquinoline) show moderate and low quantum yields in DMSO, respectively. The Stokes shift of 1 (2690 cm(-1)) is significantly smaller than those of other complexes (2, 4970; 3, 4960). A single-crystal X-ray structure analysis of 1 revealed that the three fluoride ions are coordinated meridionally. DFT calculations (B3LYP/Si, Lan2DZ; others, 6-31G**) of the complex 1 show that the main component of the HOMO is the naphthalene moiety whereas that of LUMO is the quinoline moiety.