Energy harvesting using triboelectric nanogenerators (TENGs) has demonstrated great potential in powering sensor network nodes and become a promising alternative for battery-free portable and wireless electronics. Unlike most existing rotational sliding-mode TENGs, an air-triggered contact-separation rotating triboelectric nanogenerator (AT-TENG) based on rotation-vibration-pressure conversion is proposed to reduce the violent collision of triboelectric materials and enhance the durability in this paper. The distinguishing feature of the AT-TENG was indirectly-excited contact separation mode along with the air-film interaction, where the rotational motion was converted into an elastic sheet vibration via the magnetic coupling and then the periodic contact or separation between the FEP film and aluminum plate was induced by the alternating air pressure. The feasibility of the presented AT-TENG was verified by theoretical analysis, fabrication and experiments. The results indicated that the distance of PVC to aluminum, radius ratio of the FEP to PVC, chamber volume (denoted by the acrylic ring height), magnet coefficient and rotational speed brought a significant effect on the output behaviors of the AT-TENG. There was an optimal PVC-aluminum distance of 0.1 mm as well as the maximum output voltage increased firstly and then decreased with the enhancement of radius ratio. Also, the output voltage was roughly enhanced with the increasing ring height except a maximum value occurred at h = 3.6 mm and demonstrated a reducing trend as the magnet coefficients was increased. In addition, the AT-TENG could achieve a maximum voltage of 367 V, maximum average power of 128.7 μW, and highest charging electricity of 14.45 mJ in the experiments. Besides, a parallel 200 LEDs could be efficiently powered by the AT-TENG. Furthermore, the AT-TENG demonstrated a long-term durability and stability through the 106444-excitation testing. It is expected that this work can offer a useful reference for further improvements of the rotational TENGs.