In this work single crystal fiber growth by the micro-pulling-down technique and the structural and spectroscopic characterizations of undoped and Nd³⁺-doped double molybdate LiLa(MoO₄)₂ are reported. The optimization of the growth conditions was studied in order to avoid facet formation. The grown fibers are free of scattering centers and the real dopant concentrations were confirmed to be very close to the nominal ones with a quite uniform distribution along the fibers length. The crystallographic structure concerning the scheelite tetragonal symmetries was re-evaluated. Time-resolved fluorescence spectroscopy was applied to the evaluation of some optical properties. Selective laser excitation of the ⁴F_3/2 at 875 nm and ⁴F_5/2 at 805 nm has established that the energy levels above the ⁴F_3/2 level are entirely quenched by multiphonon emission in Nd:LiLa(MoO₄)₂ crystal fiber. The potential laser gain of the system was determined using a numerical solution of the rate equations system for the 805 nm continuous pumping regime, which shows the maximum gain of the laser emission at 1.064 μm for using a Nd³⁺-doping of 5 mol%.