We report on the production of ultracold heteronuclear NaCs∗ molecules in a dual-species magneto-optical trap through photoassociation. The electronically excited molecules are formed below the Na (3S _1/2) + Cs (6P _1/2) dissociation limit. 12 resonance lines are detected using trap-loss spectroscopy based on a highly sensitive modulation technique. The highest observed rovibrational level exhibits clear hyperfine structure, which is detected for the first time. This structure is simulated within a simplified model consisting of 4 coupled levels belonging to the initially unperturbed Hund's case "a" electronic states, which have been explored in our previous work that dealt with the Na (3S _1/2) + Cs (6P _3/2) asymptote [W. Liu et al., Phys. Rev. A 94, 032518 (2016)].