In the flipped classroom, students usually conduct self-learning alone out of the class. In this situation, the students usually need appropriate guidance and peer and teacher interactions to support the self-learning. However, the students with low learning motivation may not engage in such online platforms actively and thus affect their learning performance. Therefore, appropriate learning guidance and interactive mechanisms are needed to develop for supporting the students’ self-learning process out of the class in the flipped classroom. Moreover, since the teacher can observe the students’ learning emotion and further provide appropriate learning supports to the students in the class, the teacher cannot provide such supports to the students out of the class in the flipped classroom. Therefore, it is important to the flipped classroom that is how to detect the students’ learning emotion and further provide appropriate learning supports out of the class. Bearing this in mind, this study aims to apply artificial intelligence and affective computing techniques to develop an affective awareness learning system with LINE bot for facilitating students’ self-learning out of class in the flipped classroom. To evaluate the effects of the proposed system in flipped classroom on students’ learning performance, two classes of students were invited to conducted a quasi-experiment in this study. One class served as the control group and the other class served as the experimental group. The control group was supported by traditional flipped learning strategy. The experimental group was supported by flipped learning strategy with the proposed system. The experimental results showed that the students who learned with the proposed approach outperformed those students who learned with traditional flipped learning approach in terms of learning performance, learning motivation, and problem solving ability. Moreover, the students’ learning motivation positively affects problem solving ability and learning achievement. In addition, the students’ problem solving ability showed a positively, partial mediation between learning motivation and learning achievement.