In magnetic reconnection, magnetic lines break and reconnect to change their topology to a lower-energy state. This process can liberate stored magnetic field energy and accelerate particles during unsteady explosive events. Here, we report the observations of the magnetic reconnection and kink instability of plasma jet in single wire electrical explosion and their effect on propellant ignition. The results showed that the initial velocity of plasma was ∼2,000 m/s, and when the magnetic reconnection occurred, the velocity increased by ∼400–∼2,400 m/s. The evaluated Alfvén velocity was ∼500 m/s, the Alfvén time was ∼20 µs, and the Lundquist number S = 1.7 × 107. Based on these experimental results and model, the three-dimensional magnetic field topology and its evolution process was evaluated and presented. Furthermore, the magnetic reconnection occurred when its curvature reached a certain value due to the fact that the motion of the current sheet changes the topology of the magnetic field, and then, the plasma jet was accelerated and exhausted. The plasma jet angle was ∼50° in experiment 1, and it was consistent with the calculated results. The resulting magnetic reconnection plays an important role in propellant ignition, which enhances the ignition ability of wire electrical explosion. Furthermore, the results represent a key step towards resolving one of the most important problems of plasma physics and can be used to improve the understanding of wire array explosion and propellant ignition.