Many chalcogenide compounds are formed from a diverse set of primary building blocks that include binary salts of alkali metal chalcogenides that are reacted with metals or metal salts in a variety of solutions and reaction conditions to form highly-diverse structures with varying and interesting physical properties. This review expands upon an earlier review by our group in 1997 that incorporates many of the more recent studies on the speciation of polysulfides, polyselenides, and polytellurides in aqueous and non-aqueous solutions and what has been learned in the intervening 20 years. We introduce comparisons of solution speciation across different spectroscopic platforms and provide further evidence for the use of electrospray mass spectrometry, in conjunction with complementary techniques that offer a glimpse of possible reaction compositions that lead to new materials.