We demonstrate that a near-dissociation photoassociation resonance can be used to create a deeply bound molecular sample of ultracold NaCs. To probe the resulting vibrational distribution of the sample, we use a new technique that can be applied to any ultracold molecular system. We utilize a tunable pulsed dye laser to produce efficient spectroscopic scans ($sim700$ cm$^{-1}$ at a time) in which we observe the $1^{1} Sigma^{+}rightarrow 2^{1}Sigma^{+}-2^{3}Pi$ vibrational progression, as well as the dissociation limit to the Cs 6$^{2}$P$_{3/2}$ asymptote. We assign $1^{1} Sigma^{+}$$(emph{v}$ = 4, 5, 6, 11, 19) vibrational levels in our sample.