Assembly techniques are being intensely sought for preparing nanocomposites with tunable compositions and structures. Compared to other assembly techniques, the layer-by-layer (LBL) technique, which is based on the electrostatic attraction between oppositely charged species, provides a simple, versatile and powerful method to synthesize various types of one-dimensional (1D) hybrid nanostructures. In this review, we begin with the developments in the LBL synthesis of nanocomposites, with a focus on our recent results for synthesizing 1D hybrid nanostructures via LBL assembly. Compared to previous LBL processes, we conducted the in situ reaction on the surface of 1D nanostructures via electrostatic attraction between oppositely charged 1D nanostructures and ions in the solution in an attempt to produce 1D hybrid nanostructures. Moreover, these core–shell nanostructures can be transformed into nanotubes by the removal of the templates. The as-synthesized 1D hybrid nanostructures and nanotubes with tunable composition exhibited enhanced performance for various applications such as gas sensors, lithium-ion batteries and cellular imaging.