Near-infrared (NIR) emitting phosphors with nominal formula of (Ba2−xSrx)Ca0.92Yb0.04Li0.04(Mo1−yWy)O6 (x=0–2, y=0–1) have been synthesized by solid- state reaction. Under excitation of ultraviolet (UV)-blue light, all the samples feature intense NIR emission (∼1000nm) due to the electronic transition of 2F5/2→2F7/2 of Yb3+. With Ba2+ gradually substituted by Sr2+ ions, energy transfer (ET) from MoO6 to Yb3+ becomes more efficient. Incorporation of WO6 groups causes blue shift of the charge transfer state (CTS) of MoO6 and they could act as energy obstacles to block energy quenching among MoO6 groups, resulting in more energy being transferred to Yb3+. While for W-rich phases, the intensity of Yb3+ emission decreases due to the reduced MoO6 groups. The result shows that MoO6 can be used as efficient broadband sensitization for Yb3+ and this phosphor is potentially applicable for modifying solar spectra in solar cells.