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Rare earth (RE³⁺)-doped fluorophosphate glasses are among the most promising candidates for high-efficiency laser generation in the near-infrared spectral region. By proper choice of composition, these materials can combine the advantages of fluorides (low phonon energies, low refractive indices, extensive optical window, low hygroscopicity) and of oxides (high chemical and mechanical stability and high dopant solubility), resulting in enhancement of the RE³⁺ emissive properties. In this work, we present the synthesis and structural/spectroscopic investigation of new glasses with composition 25BaF₂25SrF₂(30-x)Al(PO₃)₃xAlF₃(20-z)YF₃:zREF₃, where x = 20 or 15, RE = Er³⁺ and/or Yb³⁺, z = 0.25–5.0 mol%. Results indicate considerable improvement of the emissive properties of both ions when compared to phosphate or even other fluorophosphate host compositions. Long excited state lifetimes (τ = 10 ms …