Under 980 nm excitation, multiple ultraviolet and visible upconversion luminescence from Ho3+ and Eu3+ ions were observed in Yb3+/Ho3+/Eu3+ tri-doped NaYF4 microcrystals (MCs). The high-energy states (5H3-7, 5L6, 5D3 and 5D2) of Eu3+ ions could be efficiently populated by two-step energy transfer (ET) processes of Yb → Ho → Eu. Four-, three-, two-photon UC processes of Eu3+ ions were confirmed by the dependence of 5H3-7, 5L6 and 5D0 levels emission intensities on the pumping power.