YPO4 crystals co-doped with Tm3+ and Ho3+ ions (Tm3+/Ho3+:YPO4) have been prepared using the high temperature solution method. The crystal structure, electronic band and polarized spectroscopy were characterized. It has intense and broad absorption bands around 800 nm with a full width at half maximum of 14.31 nm and 22.95 nm for π- and σ-polarizations, respectively. Based on Judd-Ofelt theory, relevant parameters about the radiative properties were systematically analyzed. The broad emission bands of Tm3+ and Ho3+ from 1600 to 2300 nm allow wide tunability of laser oscillation. The energy transfer efficiency from Tm3+: 3F4 to Ho3+: 5I7 level in YPO4 crystal was calculated to be 54.59 %. The results show that Tm3+/Ho3+:YPO4 is expected to be applied in tunable and ultrafast pulse laser at 2.0 μm.