This research aims to investigate the effects of emotional intelligence, word-of-mouth, trust and perceived value as important psychological factors on customers’ behavior through social network online purchase. A model has been constructed and based on the proposed relationships of emotional intelligence, word-of-mouth, trust, perceived value, purchase intention and purchase decision. A survey was carried out and collected 430 responses from people who used to buy cosmetics through social networks. By using quantitative approach and verification techniques, the findings indicate that consumers’ buying behavior is predicted by word-of-mouth, trust and perceived value. Besides, word-of-mouth is also regarded as a factor that directly affects trust. In addition, there is a significant positive relationship between perceived value and trust. A positive relationship has also been found between customers’ purchase intention and their buying decision. However, there is no significant signal about the relationship between emotional intelligence and trust. The study also brings some strategic recommendations to cosmetic sellers and suppliers about how to attract more customers, and lead them to be loyal among a multitude of choices in social network online purchase.