A Tm,Ho:CaYAlO4 single crystal was grown using the Czochralski (CZ) method. The absorption spectra, the fluorescence spectrum around 2 μm, the upconversion spectrum and energy‐transfer (ET) schemes between Tm3+ ions and Ho3+ ions have been studied. The crystal boule was free from cracks, inclusions and scattering centers. The broad FWHM of the 797‐nm absorption band (with E//c polarization is 19 nm and with E//a polarization is 18 nm), the large emission bandwidth (about 600 nm) and the intense ET from Tm3+ ions to Ho3+ ions make Tm,Ho:CaYAlO4 a promising media for tunable and ultrashort pulses.