The present trend article analyzes recent progress in synthetic polymer chemistry. In particular, it emphasizes the importance of microstructural parameters such as stereoregularity and monomer sequences in polymer design allowing the preparation of highly complex ordered structures. This message is illustrated herein by examples from our laboratory and recent literature. Microstructures with different levels of complexity are presented and discussed. For instance, simple strategies such as random copolymerization of functional monomers are still relevant in current polymer chemistry. More complex microstructures such as gradient, periodic, or regulated sequence patterns are also examined.