Glass-forming region of Bi2O3-GeO2-TiO2 (BGT) pseudo-ternary system was determined by using melt-quench method. A series of high transparent glass samples were selected and their structural characteristics were investigated by FT-IR and Raman spectra. By employing Z-scan and optical Kerr shutter techniques with femtosecond laser pulses as excitation source, third-order optical nonlinearities (TON) of the BGT glasses as well as the TON response time were investigated at wavelength of 800 nm. The ultrafast nonlinear response and high figure of merit suggest great potentials of BGT glasses in applications of all-optical switching or related optical devices. (C) 2012 Elsevier B.V. All rights reserved.