Ultrashort-pulse lasers are at an increasing rate being used for laser-induced surface modification of insulators, including ablation. Ti:sapphire chirped-pulse amplifier systems, with fundamental wavelengths in the near infrared, can produce efficient ablation and other desirable surface modifications with little collateral damage because the laser energy is deposited on a time scale much shorter than thermal diffusion times. Little is known, however, about how ultrashort pulses interact with insulators at wavelengths in the vibrational infrared. This paper describes surface modifications achieved by picosecond laser irradiation in the 2 - 10 micrometer range. The laser source was a tunable, free- electron laser (FEL) with 1-ps micropulses spaced 350 ps apart in a macropulse lasting up to 4 microseconds, with an average power of up to 3 W. This unusual pulse structure makes possible novel tests of the dependence on fluence and intensity, as well as the effects of resonant vibrational excitation. As model materials systems, we studied calcium carbonate, its isoelectronic cousin sodium nitrate, and fused silica. Particularly intriguing are surface modifications achieved by tuning the laser into vibrational resonances of the target materials, or by tailoring the energy content of the pulse. The mechanisms underlying these effects, and their implications for materials-modification strategies, are discussed.