Lead sulfide nanowires with controllable optoelectronic properties would be promising building blocks for various applications. Here, we report the hot colloidal synthesis of radically branched and zigzag nanowires through self-attachment of star-shaped and octahedral nanocrystals in the presence of multiple surfactants. We obtained high-quality single-crystal nanowires with uniform diameter along the entire length, and the size of the nanowire can be tuned by tailoring the reaction parameters. This slow oriented attachment provides a better understanding of the intricacies of this complex nanocrystal assembly process. Meanwhile, these self-assembled nanowire structures have appealing lateral conformations with narrow side arms or highly faceted edges, where strong quantum confinement can occur. Consequently, the single-crystal nanowire structures exhibit strong photoluminescence in the near-infrared region with a large blue-shift compared to the bulk material.