The vibrational modes of the deoribase-phosphodiester backbone moiety of DNA and their interactions with the interfacial aqueous environment,are addressed With two-dimensional (2D) infrared spectroscopy on a femto- to picosecond time scale. Beyond, the, current understanding in the harmonic approximation, the anharmonic,character and delocalization of the backbone modes in the frequency range from 900 to 1300 cm(-1) are determined with both diagonal anharmonicities and intermode coupling on the order of 10-cm(-1). Mediated by the intermode couplings, energy, transfer between the backbone modes takes place on ea picosecond time scale, parallel to vibrational relaxation and energy dissipation into the environment. probing structural dynamics noninvasively via the time evolution of the lineshapes, limited structural fluctuations are observed on a 800 fs tine scale of low-frequency motions Of the counterions, and water shell. Structural disorder of the DNA-water interface and DNA-water hydrogen bonds are, however, preserved for times beyond 10 ps. The different interactions Of limited strength ensure ultrafasts vibrational relaxation and dissipation of excess energy in the backbone structure, processes, that ate important for the structural integrity of hydrated DNA.