This article describes the use of optical methods based on picosecond transient gratings to stimulate and detect ultrasonic acoustic modes in several important structures with dimensions less than ∼200 μm: single-mode optical fiber, cylindrical microcapillary tubes, and planar microfluidic networks. The measurements illuminate the characteristics and dispersion of acoustic modes—Rayleigh and Lamb-like modes and Scholte–Stoneley waves—in three-dimensional microsystems with feature sizes that are comparable to the modal wavelengths. The results demonstrate, for example, the ability to measure, rapidly and nondestructively, the mechanical characteristics of on-fiber metal and polymer coatings. They also illustrate real-time monitoring of the elastic and loss moduli, and thermal diffusivities of nanoliter volumes of material contained in planar microfluidic channels during the course of photochemical curing reactions. The techniques are potentially useful for applications ranging from characterization of high-frequency acoustic modes in optical fiber that may be relevant to new types of in-fiber acousto-optic filters and modulators, to detection in microfluidic total analysis systems.