Along with the rapid development of micro/nanofabrication technology, the past few decades have seen the flourishing emergence of subwavelength-structured materials and interfaces for optical field engineering at the nanoscale. Three remarkable properties associated with these subwavelength-structured materials are the squeezed optical fields beyond the diffraction limit, gradient optical fields in the subwavelength scale, and enhanced optical fields that are orders of magnitude greater than the incident field. These engineered optical fields have inspired fundamental and practical advances in both engineering optics and modern chemistry. The first property is the basis of sub-diffraction-limited imaging, lithography, and dense data storage. The second property has led to the emergence of a couple of thin and planar functional optical devices with a reduced footprint. The third one causes enhanced radiation (e.g., fluorescence), scattering (e.g., Raman scattering), and absorption (e.g., infrared absorption and circular dichroism), offering a unique platform for single-molecule-level biochemical sensing, and high-efficiency chemical reaction and energy conversion. In this review, we summarize recent advances in subwavelength-structured materials that bear extraordinary squeezed, gradient, and enhanced optical fields, with a particular emphasis on their optical and chemical applications. Finally, challenges and outlooks in this promising field are discussed.