As a rising social network sitting platform，the live video stream is attracting a huge amount of audience. Since the live video stream industry has a very rapid development，the public has little knowledge to understand it. So far，there is no academic research concerning this phenomenon. In order to fill this literature gap，this study investigates effects of live video stream on audience’s psychological well-being via an exploratory approach. This study adopted the subject well-being as the indicator of psychological well-being and made use intensity and motivation into consideration. Through a college student population survey，this study found that use of live video stream is positively associated with subject well-being. The association is also mediated by motivation，especially external motivation which can be understood that the subject well-being from the use of live video stream for college students is affected by external social networks. Future studies should concern more population and other psychological well-being indicators to elaborate the whole pattern of effects from live video stream on audience.