Eu~ 3+ was incorporated as probe ions into nanocomposite glasses, such as metal silver doped phosphate glass and crystalline nanocomposites Si-enriched SiO_2 glass. Luminescence studies show that the doped europium ions are present as trivalent Eu~ 3+ , and are distributed in the matrix on the boundary surface of nanoparticles. The valence switching from Eu~ 3+ to Eu~ 2+ was observed in Si-SiO_2 nanocomposites when ultrafast laser excitation was applied. In silver metal nanoparticles embedded aluminophosphate glass, a time-resolved ultrafast degenerate-four-wave-mixing (DFWM) experiment shows enhanced third-order nonlinearity at zero-delay time, followed by a bell-like signal buildup. It is attributed to the creation of electronic polaron and vibronic Wannier-Mott exciton (WME). In europium codoped sample, however, the bell-like signal is depressed. All the above observations are interpreted as the result of a strong Coulomb interaction between conduction electrons produced inside the nanoparticles by laser excitation and Eu~ 3+ ions residing near the boundary surface. The trivalent europium ions play the role as positive charges attracting electrons. This results in temporary formation of Eu~ 2+ , and blocks the resonant tunneling transition in the silver-glass system to avoid creating large radius polaron. Eu ~ 3+ was incorporated as probe ions into nanocomposite glasses, such as metal silver doped phosphate glass and crystalline nanocomposites Si-enriched SiO 2 glass. Luminescence studies show that the doped europium ions are present as trivalent Eu ~ 3+, and are distributed in The matrix on the boundary surface of nanoparticles. The valence switching from Eu ~ 3+ to Eu ~ 2+ was observed in Si-SiO_2 nanocomposites when ultrafast laser excitation was applied. In silver metal nanoparticles embedded aluminophosphate glass, a time-resolved ultrafast degenerate -four-wave-mixing (DFWM) experiment shows enhanced third-order nonlinearity at zero-delay time, followed by a bell-like signal buildup. It is attributed to the creation of electronic polaron and vibronic Wannier-Mott exciton (WME). All the above observations are interpreted as the result of a strong Coulomb interaction between the transmitted electrons produced inside the nanoparticles by laser excitation and Eu ~ 3+ ions residing near the boundary surface. The trivalent europium ions play the role as positiveperspending attracting electrons. This results in temporary formation of Eu ~ 2+, and blocks the resonant tunneling transition in the silver- glass system to avoid creating large radius polaron.