Multi-robot systems have been extensively studied and the coordination among the robots becomes a hotspot. Among the typical research tasks of multi-robot system, coordinated hunting with unknown irregular motion of the evader or target has attracted more and more attentions due to its potential application to military, safe guard etc. The spiking neural network (SNN), considered as the third generation of neural network (Maass & Bishop, 1999), has attracted many attentions. Spikes (pulses) are used to deliver the information between neurons, i.e. SNN processes the information in the form of spikes, which brings temporal structure and extends the functionality of SNN (Kasabov, 2010). Besides the rate coding, inspired by the results of biological experiments, some coding strategies based on spike timing have been proposed, such as time-to-first-spike coding, phase coding, correlations/synchrony coding et al. (Maass & Bishop, 1999). Also, Maass et al. present some useful spiking neuron models, such as spike response model (SRM), integrate-and-fire model (IF), Hodgkin-Huxley Model and so on (Maass & Bishop, 1999). For these coding methods and neuron models, the Hebb learning is proposed to adapt the weights between neurons based on the temporal difference between input and output spikes (Kempter et al., 1999). Nowadays, the controllers based on SNN have been introduced to many applications, such as phase/frequency correlations recognizing (Kiselev, 2009), movement prediction from real-world images (Burgsteiner et al., 2005), movement generation of the robot arm (Joshi & Maass, 2005), etc. Especially, SNN has been applied to the control of the mobile robot (Floreano & Mattiussi, 2001; Roggen et al., 2003; Hagras, 2004; Qu et al., 2009). In this chapter, a robot controller based on spiking neural network (SNN) is proposed for the coordinated hunting of multi-robot system. The controller utilizes 12 direction-sensitive modules to encode and process the inputs including the environment, target and coordination information by the time-to-first-spike coding and then, the motor neurons generate the control signals for the motors according to the winner-take-all strategy. Also, the Hebbian learning with a stochastic form is applied to adjust the connection weights. The rest of the chapter is organized as follows. In Section 2, the structure of the controller is given and the inputs encoding, coordination between robots and motor neurons are