There is strong demand for effective gain materials for the 3.0-3.9 μm spectral range not nicely covered by Cr:ZnSe and Fe:ZnSe amplification bands. We characterized, Fe:ZnAl2O4 ceramic sample, Fe:MgAl2O4 and Fe:InP single crystals as promising laser materials for this mid-IR spectral range. In all crystals, the absorption bands corresponding to 5E↔5T2 transition of Fe2+ ions in the tetrahedral sites were measured. In addition, absorption band of Fe2+ ions in the octahedral sites were observed in Fe:ZnAl2O4 sample with maximum absorption cross-section at ~1.0 μm. From the absorption measurements, the radiative lifetime of Fe:MgAl2O4 was calculated to be 60 μs. Saturation absorption of Fe2+ ions in Fe:ZnAl2O4 was studied using Ho:YAG@2.09 μm and Er:YAG@2.94 μm lasers. Saturation measurements were taken up to energy density of 2 J/cm2 and showed no saturation of absorption. This can be explained by a fast non-radiative (<100 ps) relaxation time from the 5T2 level of Fe2+ ions in the Fe:ZnAl2O4 sample at RT. A strong mid-IR photoluminescence (PL) signal in Fe:InP crystal was detected under the direct excitation of the 5E↔5T2 transition of Fe2+ ions using Er:YAG@2.94 μm laser as well as excitation using photo-ionization process under radiation from Nd:YAG@1.064 μm laser. This indicates that Fe:InP crystals could become promising mid-IR laser media with optimization of fabrication technology.