Spectroscopic properties of erbium (Er 3+ )-, holmium (Ho 3+ )-, dysprosium (Dy 3+ )-doped and Er 3+ /Ho 3+ , Er 3+ /Dy 3+ co-doped ZBLAN (ZrF 4 -BaF 2 -LaF 3 -AlF 3 -NaF) glasses were studied. The experimental results show that efficient energy transfer from Er 3+ to Ho 3+ and Dy 3+ occurs in the Er 3+ /Ho 3+ and Er 3+ /Dy 3+ co-doped ZBLAN glasses, respectively. This valuable discovery enables us to design and develop high power Ho 3+ -doped and Dy 3+ -doped ZBLAN fiber lasers in the 3 µm wavelength region that can be pumped with readily available high-efficiency, high-power diode laser pumps at 980 nm.