Due to the limitations of the existing measurements of experiential avoidance, we would like to check the validity of the improved version of Acceptance and Action Questionnaire–II (AAQ-II), i.e., Acceptance and Action Questionnaire–3 (AAQ-3), in Chinese content. The present study was aim to examine the construct and validity of the Chinese version of AAQ-3 in college students and provide an initial validation of this instrument to promote future cross-cultural examination of the psychological flexibility. Totally 1,572 college students were invited to complete the Chinese AAQ-3 and the related questionnaires at the same time. After one month, 380 participates were assessed with same questionnaires to examine the test-retest reliability. The results indicated a similar one-factor solution in the Chinese AAQ-3 to the original version by exploratory factor analysis, parallel analysis and confirmatory factor analysis. Internal consistency and test–retest reliability were good. According to the testing of the measurement invariance, the one-factor model was acceptable across gender (Man = 875, Girl = 697). Additionally, Chinese AAQ-3 was significantly negatively correlated with positive mental health (life satisfaction, mindful attention awareness), significantly positively correlated with negative emotions (depression, anxiety, stress), and significantly positively correlated with AAQ–II and Brief Experiential Avoidance Questionnaire (BEAQ). Besides, Chinese AAQ-3 was the strongest predictor of depression, anxiety, stress and life satisfaction compared to the AAQ-II and BEAQ. However, according to the exploratory structural equation model, the Chinese AAQ-3 demonstrated excellent discriminate validity from negative emotions. Overall, the AAQ-3 modified the limitations of the existing measurements of experiential avoidance (i.e., AAQ-II and BEAQ) as it showed better convergent validity with positive mental health indicators, better discriminant validity with negative emotions, and higher incremental validity. Therefore, the Chinese AAQ-3 is a valid measurement tool for assessing the level of experiential avoidance or psychological flexibility in Chinese college students.