Recrystallization of tooth dentin by the application of mid- infrared (MIR) pulsed-laser irradiation is one candidate for a novel, non-invasive treatment for the prevention of tooth decay. Recrystallized dentin functions in a similar way to dental enamel. To recrystallize the dentin effectively and non-invasively it is essential to estimate quantitatively and qualitatively the laser parameters, such as the wavelength and the average power density, required for recrystallization. The laser-tissue interaction is initiated effectively by selective excitation of phosphate acid ions (PO4) in the dentin. Using a tunable, MIR Free Electron Laser (FEL) in the wavelength region of 8.8- 10.6micrometers , corresponding to intense absorption bands due to PO4 vibration modes, we have investigated macroscopically extent of surface modification of dentin, and we have obtained experimental results related to the ablation depth, the MIR absorption spectrum, and the elemental chemical composition. From these results, it was found that (1) the laser parameters at which efficient surface modification, without enhanced ablation effects, occurred were estimated to be approximately in the wavelength and average power density regions of ~9.4- 10.3micrometers and ~10-20 W/cm2, and that (2) in this region PO4 vibration modes with lower binding energy were preferentially excluded from the dentin.