Two sets of Er 3+ -doped alkaline-free glass systems, MgF 2 –BaF 2 –Ba(PO 3 ) 2 –Al(PO 3 ) 3 (MBBA) and Bi(PO 3 ) 3 –Ba(PO 3 ) 2 –BaF 2 –MgF 2 (BBBM), have been prepared and investigated with the aim of using them as active media. Radiative lifetimes (τ rad ) and branching ratios (β) have been obtained for the excited states of Er 3+ . The absorption spectra were recorded to obtain the intensity parameters (Ω t ) which are found to be Ω 2 =4.47×10 −20 cm 2 , Ω 4 =1.31×10 −20 cm 2 , Ω 6 =0.81×10 −20 cm 2 for the MBBA system and Ω 2 =4.03×10 −20 cm 2 , Ω 4 =1.34×10 −20 cm 2 , Ω 6 =0.53×10 −20 for the BBBM system, respectively. The emission cross-section for the 4 I 13/2 → 4 I 15/2 transition is determined by the Fuchtbauer–Ladenburg method and found to be 2.35×10 −20 cm 2 and 3.54×10 −20 cm 2 for the MBBA and BBBM system, respectively. Comparison of the measured values to those of Er 3+ transitions in other glass hosts suggests that our new glass systems are good candidates for broadband compact optical fiber and waveguide amplifier applications.