We demonstrate that a photoassociation resonance detuned less than a wave number below the Cs
62P3/2 atomic line can be used to create a deeply bound molecular sample of ultracold polar NaCs. We assign $1 {}^{1}{\ensuremath{\Sigma}}^{+}$ (
v=4,5,6,11,19) vibrational levels utilizing a pulsed depletion spectroscopic method (scanning
700 cm${}^{\ensuremath{-}1}$ at a time) in which we observe the $1 {}^{1}{\ensuremath{\Sigma}}^{+}\ensuremath{\rightarrow}2 {}^{1}{\ensuremath{\Sigma}}^{+}\ensuremath{-}1 {}^{3}\ensuremath{\Pi}$ vibrational progression. These data are compared with results from a hot-molecule collision-enhanced laser-induced fluorescence experiment and shown to be in good agreement. This technique is a powerful tool to experimentally determine the population distribution in any ultracold molecular system.