Block copolymers form the basis of the most ubiquitous materials such as thermoplastic elastomers, bridge interphases in polymer blends, and are fundamental for the development of high-performance materials. The driving force to further advance these materials is the accessibility of block copolymers, which have a wide variety in composition, functional group content, and precision of their structure. To advance and broaden the application of block copolymers will depend on the nature of combined segmented blocks, guided through the combination of polymerization techniques to reach a high versatility in block copolymer architecture and function. This review provides the most comprehensive overview of techniques to prepare linear block copolymers and is intended to serve as a guideline on how polymerization techniques can work together to result in desired block combinations. As the review will give an account of the relevant procedures and access areas, the sections will include orthogonal approaches or sequentially combined polymerization techniques, which increases the synthetic options for these materials.