Vibrational overtone-overtone double resonance combined with vibrationally mediated photodissociation is used to access highly excited vibrational states of water in the region of 22 000-25 000 cm(-1) with good sensitivity. The double resonance aspect of the vibrational excitation process allows us the ability to access vibrational states of different symmetry than possible through direct absorption. In addition, the technique provides the means to examine state resolved photodissociation dynamics of this prototypical molecule from strongly mixed vibrational states as well as study collisional relaxation in this system.