The sleep and arousal, or the vigilance state, is controlled by a highly dynamic brain system that involves numerous interconnected brain circuits. However, while many reviews presented the anatomical bases of how different components of the brain area contribute to the vigilance states, less attention is paid from the perspective of different neurotransmitters. As multiple different neuronal populations could exist and express in the same brain area, attributing the effect of different brain areas on sleep and arousal would not be precise without consideration of the act of neurotransmitters. This review summarizes the recent progress on how different neurotransmitters affect vigilance states. By doing so, this review aims to provide an alternative angle in understanding how different vigilance state is regulated by the brain.