Organoselenium and organotellurium compounds are increasingly important in synthetic, biological, and materials chemistry. Their unique chemical behavior has positioned 77Se and 125Te NMR spectroscopy as valuable tools for structural and stereochemical analysis. 77Se NMR is particularly powerful due to its favorable nuclear properties, including a natural abundance of 7.5%, spin ½, and sensitivity higher than 13C. One of its greatest advantages is an exceptionally wide chemical shift range of about 3400 ppm, which enables clear signal separation and reliable identification of stereochemical differences, including chiral discrimination. Chemical shifts are typically referenced to diphenyl diselenide (δ = 463 ppm). Similarly, 125Te NMR offers complementary analytical strength with comparable nuclear characteristics and a broad spectral window. Both nuclei are highly responsive to changes in electronic and steric environments, making them effective for monitoring subtle configurational and conformational variations. Together, 77Se and 125Te NMR provide advanced spectroscopic platforms for stereochemical assignment, mechanistic investigation, and chiral recognition in main-group element chemistry. This chapter summarizes their analytical advantages and growing applications in the study of chiral systems.