Cryolite was considered to be an ideal up-conversion host material due to its low phonon energy, which can effectively suppress the radiation-free transition process of excited state energy levels. In the present paper, a novel up-conversion material K3YF6:Ho3+, Yb3+ with cryolite structure was prepared successfully using a high-temperature solid state method. The up-conversion luminescence properties of K3YF6 doped with different Ho3+/Yb3+ doping ratio were investigated and the optimal doping ratio were confirmed in this system. Under 980 nm excitation, Ho3+/Yb3+ co-doped K3YF6 revealed a strong green emission at the 541 nm, 549 nm and a weak red emission peaking at 666 nm, corresponding to the 5F4, 5S2→5I8 and 5F5→5I8 transitions of Ho3+, respectively. All the red and green up-conversion emission of K3YF6:Ho3+, Yb3+ belong to two-photon process and energy transfer from Yb3+ to Ho3+ simultaneously. Additionally, to understand the energy transfer and electronic transition process of the red and green light emitted, the possible luminescence mechanism were also analyzed in this paper. All the results indicate that Ho3+/Yb3+ co-doped K3YF6 have potential application value in green up-conversion luminescent materials.