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Eu-doped silicon-rich silicon oxide (SRSO) films on P (100) Si substrate were deposited by electron beam evaporation (EBE). The effect of annealing procedure on the photoluminescence (PL) has been investigated in detail. Experimental results show that after 1100degC annealing at non-reductive atmosphere, the films are revealed to yield an intense broad band yellow light emission. PL spectra of the broad yellow band are centered at about 530 nm which agrees with 4f65d-4f7(8S7/2) transition of divalent europium ions (Eu2+). And the existence of Eu2+ has been further confirmed by XPS measurement results.