Spectroscopic investigations are made on new laser monoclinic single-centered LiKYF5: Nd3+ crystals grown by the hydrothermal method. Stark levels of its activator ions for 37 2s+1LJ manifolds lying up to ≈ 40000 cm−1 are established from luminescence and absorption spectra at 7 K. Using a new set of reduced-matrix elements for electric-dipole 4f3−4f3 transitions the intensity characteristics for LiKYF5: Nd3+ are calculated including phenomenological Judd-Ofelt parmaeters Ω1, intermanifold absorption line strengths, as well as the radiative lifetime of the initial laser state 4F3/2 and branching ratios originated for its IR emitting channels. The kinetics of luminescence from four metastable states 2F(2)5/2, 4D3/2, 2P3/2, and 4F3/2 as function of Nd3+-ion concentration and temperature are measured. Room-temperture pulse, cw, and quasi-cw stimulated emission of Nd3+ ions at two generating 4F3/2 → 4I11/2 and 4F3/2 → 4I13/2 channels under Xe-flashlamp and laser-diode pumpings are obtained. All observed induced inter-Stark transitions are identified.