The semiconductors Li2CdGeS4 and Li2CdSnS4, which are of interest for their nonlinear optical properties, were synthesized using high-temperature solid-state and polychalcogenide flux syntheses. Both compounds were found to crystallize in Pmn2(1), with R1 (for all data) = 1.93% and 1.86% for Li2CdGeS4 and Li2CdSnS4, respectively. The structures of both compounds are diamond-like with the tetrahedra pointing in the same direction along the c axis. The alignment of the tetrahedra results in the structure lacking an inversion center, a prerequisite for second-harmonic generation (SHG). A modified Kurtz nonlinear optical powder technique was used to determine the SHG responses of both compounds. Li2CdGeS4 displayed a type 1 phase-matchable response of approximately 70x alpha-quartz, while Li2CdSnS4 displayed a type I non-phase-matchable response of approximately 100x alpha-quartz. Diffuse-reflectance spectroscopy was used to determine band gaps of 3.10 and 3.26 eV for Li2CdGeS4 and Li2CdSnS4, respectively.