Lithium containing semiconductor-grade chalcogenide single crystals were grown using the vertical Bridgman method. The source material was synthesized from elementary precursors in two steps, (i) preparing the metal alloy LiIn or LiGa, and (ii) reaction with chalcogen – Se or Te. In a number of experiments, enriched 6Li isotope was used for synthesis and growth. The composition and structure of the synthesized materials was verified using powder X-Ray diffraction. The energy band gaps of the crystals were determined using optical absorption measurements. The resistivity of LiInSe2 and LiGaSe2, obtained using current–voltage measurements is on the order of 108–1011 Ω cm. Photoconductivity measurement of a yellow LiInSe2 sample showed a peak in the photocurrent around 445 nm. Nuclear radiation detectors were fabricated from single crystal wafers and the responses to alpha particles, neutrons and gammas were measured and presented. It suggests that this material is a promising candidate for neutron detection applications.