In this chapter, the authors summarize state-of-the-art dual-layer and multibore hollow fiber (MBF) membranes for membrane distillation applications. In the first part, three major types of dual-layer designs, namely, (1) morphologically controlled dual-layer membranes, (2) dual-layer membranes with enhanced mechanical integrity, and (3) hydrophobic/hydrophilic dual-layer membranes, will be introduced. The rationale, design, formation mechanism, challenges, and advantages of these three types of dual-layer membranes will be discussed in detail. In the second part, various types of multibore membranes will be introduced. Technological know-hows of fabricating MBF membranes and the advantages and challenges of different membrane geometries will be elaborated.