Internal energy distribution of the NO product from photodissociation of t-butyl nitrite in the region between 220 and 250 nm are presented. The rotational distribution for all the vibrational levels are similar throughout the region, with a dominant Gaussian-like highly rotationally (J) excited component and a minor low-J component. Increase in the dissociation energy has a dramatic effect on the vibrational distribution: at 250 nm, the upsilon" = 0 channel dominates, while at 220 nm, the upsilon" = 0 channel is undetectable using our apparatus. These observations reveal new information on the S-2 surface and the dissociation dynamics of t-butyl nitrite.