**Abstract**

Since the discovery of Ziegler-Natta catalysts for olefin polymerization in the 1950s, the production of polyolefins with a variety of properties has continuously grown with rapid development of catalyst technology combined with polymerization process innovation. For propylene-based polyolefin, various polyolefins with distinctive characteristic of mechanical and optical properties were made with specific catalysts in commercial industries owned especially by those large worldwide companies. In this chapter, Ziegler-Natta catalysts, metallocene catalysts, and post-metallocene catalysts for PP polymerization are discussed in detail. Gas phase, bulk, slurry, and solution polymerization processes, such as Spheripol (Basell), Hypol (Mitsui Chemicals), Unipol (Dow Chemical), Innovene (INEOS), Novelen (BASF), Spherizone (Basell), and Borstar (Borealis), developed by the industrial tycoons were reviewed. The molecular architecture of the PP-based polyolefins could be tailored precisely using specific high-performance catalyst in an appropriate polymerization process, and different types of PPs, including homopolypropylene (HPP), random copolypropylene (RPP), impact PP, PP-based block copolymer, functionalized PP, etc., are produced. The relationship between molecular structure and performance of the PP-based polyolefins is also discussed thereof.

**Keywords:** polymerization process, propylene-based polyolefin, polypropylene, Z-N catalyst, metallocene, post-metallocene
