Sulfur-containing compounds, particularly derivatives of thiophene, are well studied for organic optoelectronic applications. Incorporating selenium or tellurium in place of sulfur imparts different physical properties due to the fundamental differences of these atoms relative to their lighter analogues. This has a profound influence on the properties of molecules and materials that incorporate chalcogens that may ultimately lead to new opportunities and applications. This mini-review will focus on the quantitative and qualitative photophysical characteristics of organic materials containing selenium and tellurium as well as their emerging applications as molecular photoactive species, including light-emitting sensors, triplet sensitizers, and beyond. Incorporating selenium or tellurium into photoactive species imparts new photophysical properties that may be exploited in materials applications.