Mid-infrared (MIR) emissions of 2.4 and 3.5 m from Tm3+:LiYF4 single crystals attributed to 3H4->3H5 and 3H5->3F4 transitions as well as MIR emissions of 4.2, 4.3, and 4.5 \mu m from Nd3+: LiYF4 lasers attributed to 4I15/2->4I13/2,4I13/2->4I11/2, and 4I11/2->4I9/2 transitions, respectively, are observed. LiYF4 single crystals possess high transmittance of over 85% in the 2.5-6 \mu m range. The large emission crosssections of Tm-doped crystals at 2.4 \mu m (1.9\times 10-20 cm2) and Nd-doped crystals at 4.2 \mu m (0.84\times 10-20cm2) as well as the high rare-earth doping concentrations, excellent optical transmission, and chemicalphysical properties of the resultant samples indicate that Nd3+ and Tm3+ singly doped crystals may be promising materials for application in MIR lasers.