Nanostructured materials have become an increasingly important theme in research, in no small part due to the potential impacts this science holds for applications in technology, including such notable areas as sensors, medicine, and high-performance integrated circuits. Conventional methods, such as the top-down approaches of projection lithography and scanning beam lithography, have been the primary means for patterning materials at the nanoscale. This article provides an overview of unconventional methods -both top-down and bottom-up approaches -for generating nanoscale patterns in a variety of materials, including methods that can be applied to fragile molecular systems that are difficult to pattern using conventional lithographic techniques. The promise, recent progress, advantages, limitations, and challenges to future development associated with each of these unconventional lithographic techniques will be discussed with consideration given to their potential for use in large-scale manufacturing.