Rare-earth ion-doped semiconducting phosphor has attracted extensive attention due to the ability to achieve efficient luminescence through the host sensitization. Here, we present a new type red-emitting Eu3+-doped BiOCl phosphors possessing a broad excitation band in the near-ultraviolet (NUV) region. Experimental measurements and theoretical calculations confirm that Eu3+ ion dopants result in forming impurity energy level near valence band, and the excellent broadband NUV-exciting ability of Eu3+ ion is due to the electronic transitions of BiOCl band gap. Moreover, the highest emission intensity of the phosphors is from the D-5(0) F-7(4) transition of Eu3+ around 699nm (far-red) through whether host excitation or direct Eu3+ ions excitation, which lie in the particular structure of BiOCl crystals. Our results indicate that the Eu3+-doped BiOCl crystals show great potential as red phosphors for white-light-emitting diodes.