The second class of high-temperature superconductors （HTSCs）, iron-based pnictides and chalcogenides, necessarily contain Fe2X2 （＂X＂ refers to a pnictogen or a chalcogen element） layers, just like the first class of HTSCs which possess the essential CuO2 sheets. So far, dozens of iron-based HTSCs, classified into nine groups, have been discovered. In this article, the crystal-chemistry aspects of the known iron-based superconductors are reviewed and summarized by employing ＂hard and soft acids and bases （HSAB）＂ concept. Based on these understandings, we propose an alternative route to exploring new iron-based superconductors via rational structural design.
