This chapter gives a perspective on the evolution of catalyst systems for the stereoregular polymerization of higher α-olefins (CH2=CHR, where R ≥ CH2CH3). Heterogeneous systems, metallocene systems, and nonmetallocene systems (including amine-phenolate catalyst systems introduced by the Kol research group) are reviewed. In general, the mechanisms controlling chain growth, regioregularity, and stereoregularity that apply to propylene polymerization also apply for higher α-olefin polymerization, so they will not be discussed in detail in this chapter.