In this communication, we describe the sequential deposition of materials in capillaries as a means to produce self-assembled three-dimensional gold microtubes, hollow gold microwires, and microtube and microwire arrays with unprecedented aspect ratios. The initial application of this technique is the fabrication of an array of microwires within a silica capillary array. The physical characteristics of these microwires are characterized via SEM, electrochemistry, and electrogenerated chemiluminescence emission.