We report new observations of the hyperfine structure in three ro-vibrational levels of the b3Π2 state of NaCs near the dissociation limit 3S1/2 + 6P3/2. The experiment was done via photoassociation of ultracold atoms in a dual-species dark-spot magneto-optical trap, and the spectra were measured as atomic trap losses. The simulation of the hyperfine structure showed that the greater part of the observed structure belongs to almost isolated levels of the b3Π2 state, but there are other parts of mixed character where the contribution from the 1Σ symmetry dominates.