A Raman signal-enhancing structure includes a substrate and a plurality of protrusions located at predetermined positions relative to a surface of the substrate. Each protrusion includes a Raman signal-enhancing material and has cross-sectional dimensions of less than about 50 nanometers. The structure also includes an edge that includes an intersection between two nonparallel surfaces of at least one protrusion. A Raman spectroscopy system includes such a Raman signal-enhancing structure, and Raman spectroscopy may be performed on an analyte using such structures and systems. A method for forming such a Raman signal-enhancing structure includes nanoimprint lithography.