This study aims to integrate the technology acceptance model, classroom environment theory, and positive psychology theory to explore the relationships among learners' technology acceptance (TA), perceived online classroom environment (POCE), emotional states (enjoyment, anxiety, boredom, and burnout), and academic achievement in online classes. Six hundred and sixty-two university students learning Chinese as a foreign language participated in the survey and completed the reading test. The results of partial least square-structural equation modeling reveal that TA influences reading achievement directly and indirectly through anxiety (with the reversed mediating effect) and enjoyment, and the online classroom environment mediated the relationship between TA and learning emotions (except anxiety). These findings suggest that technology factors may shape the affordance of online classrooms and penetrate environmental and emotional variables to impact FL learning outcomes. Multigroup analysis with different self-online learning time underscores that enjoyment and anxiety differ in two different effect paths (POCE-enjoyment) and (TA-anxiety), implying enjoyment may be more environment-related while anxiety may be more technology-related in the online foreign language classroom. This study provides both theoretical and pedagogical implications.