Li-based semiconductor materials represent a promising alternative to 3-He and scintillation materials for thermal neutron detection and imaging instruments. Semiconductor crystals of LiInSe2, LiInP2Se6, and LiGaInSe2 (LiGa0.5In0.5Se2) were grown using natural and enriched lithium ( 6 Li). The materials were characterized for electronic and optical properties including optical transmission, current-voltage (I-V) characteristic for resistivity, and bandgap. Thermal neutron detectors were fabricated and characterized for neutron and gamma-ray response. Pulse height spectra were collected from a moderated custom-designed 241 AmBe neutron source and a 60 Co gamma-ray source. The LiInSe2 samples exhibited a 2.8 eV cutoff in the optical spectrum and a resistivity of ~8×10 11 Ω•cm. LiInSe2 devices exhibit a noise floor of <30 keV which operated at a field of 630 V/mm, for the 0.8-mm thick device. The Vertical Gradient Freeze (VGF) grown LiInP2Se6 samples exhibited a 2.2 eV cutoff in the optical spectrum and resistivity of ~4×10 12 Ω•cm. The Chemical Vapor Transport (CVT) grown LiInP2Se6 devices exhibit a noise floor of <60 keV which operated at a field of 8,000 V/mm, for the 0.05mm thick device. Furthermore, the long-term stability of LiInSe2 devices during multiple weeks under continuous bias was investigated.