As laser micromachining is applied to ever smaller structures and more complex materials, the demand for greater control of the laser energy budget, in space and time, grows commensurately. Here we describe materials modification using picosecond resonant laser excitation in the mid-infrared spectral region to create spatially and temporally dense vibrational, rather than electronic, excitation. Examples include ablation of fused silica and machining of crystalline quartz; deposition of functionalized polymers on microstructures, and laser-directed transfer of proteins and nucleotides from a matrix of water ice. The experiments demonstrate that high spatial and temporal density of vibrational excitation can be achieved by ultrafast resonant infrared excitation of selected vibrational modes of these materials. In some cases, resonant infrared materials modification is far more successful than techniques based on ultraviolet excimer lasers. The laser used for most of the experiments was a tunable, high pulse-repetition frequency free-electron laser. However, a comparison of polymer deposition using a conventional nanosecond laser at a wavelength of 2.94 μm shows that the possibility exists for transferring the concept to conventional table-top devices. Mechanistic considerations nevertheless suggest that utlrashort pulses are likely to be more useful than longer pulses for many applications. A figure of merit is proposed for self-consistent comparisons of processing efficiency among different lasers.