Strong L-S coupling effect of the paramagnetic center Ti3+ ions in Ti:Al2O3 crystal allows the observation of electron spin resonance (ESR) absorption spectra of Ti3+ ions only at about the liquid helium temperature.Spectra with steep peaks of impruity ions superposed on the extremely broadened Ti3+ ion absorption lines have been observed at 93 K. Spin transitions occurring within the respective ground states of Fe3+,Mn2+, Cr3+,Mo3+,Fe2+,Co2+ etc.impurity ions and Ti2+ ions double-quantum transition, as well as Ti isotopes hyperfine splittings are assigned.