One-color two-photon excitation spectra of the 4f1 → 5d1 transitions of Ce3+ in LiYF4 have been investigated at 5 K from 33 400 to 44 000 cm−1. A sharp lorentzian line peaking at 33 439.4 cm−1 with a width of 2.6 cm−1 is observed on the low energy side of a band extending up to 35 200 cm−1. The line and the band are observed to exhibit different polarization dependences. A second band with a maximum peaking around 41 977 cm−1 is observed to extend from 40 000 up to 44 000 cm−1. No sharp line associated to this band is seen