Colloidal lithography (CL) is a newly developing nanofabrication technique and can produce various nanostructures at low cost and large scale. The CL‐based nanostructures offer great performances in plasmonics, which holds a unique capability to concentrate light into subwavelength volumes. Valuable physics effects accompanied with plasmonics, such as heat generation, optical near‐field enhancement, and excitation of hot electrons have been verified to benefit chemistry reactions, leading to a new field of plasmonic nanochemistry. Starting from CL, by way of plasmonic nanostructures, toward chemistry reaction, it shows a powerful strategy to develop all these three research areas, like the silk road which has a wide profit. In this scenario, a nanoscale “silk road” from CL to plasmonic nanochemistry is presented. Recent plasmonic nanostructures fabricated via CL are summarized and are morphologically classified into multilayer, hierarchical, hollow, asymmetric, and other nanostructures. Mechanism and development of plasmonics nanochemistry are introduced. Application prospects of several unique CL‐based structures will be expected. Finally, challenges and perspectives are offered to inspire more ingenious developments of using CL in plasmonic nanochemistry.