Little is known about the mechanisms underlying the relation between perceived teacher emotional support and intrinsic motivation to learn English. The primary purpose of this quantitative, cross-sectional correlation study was to examine the mediating effects of foreign language enjoyment, anxiety, and self-efficacy on the relationship between Chinese college students’ perceptions of teacher emotional caring and intrinsic motivation in EFL classrooms. Undergraduates (N = 1,464) enrolled in six public four-year universities in mainland China completed five student self-report questionnaires. Data were analyzed using an ordinary least squares (OLS) regression-based path analysis with the PROCESS macros for SPSS and utilizing the Amos program version 26.0 for structural equation modeling (SEM) with maximum likelihood method. Five specific indirect effects of emotional support from teachers on intrinsic motivation to learn English were tested. Specifically, the five indirect effects (or mediating) pathways were hypothesized as: (1) teacher emotional support to enjoyment to intrinsic motivation, (2) teacher emotional support to anxiety to intrinsic motivation, (3) teacher emotional support to self-efficacy to intrinsic motivation, (4) teacher emotional support to enjoyment to self-efficacy to intrinsic motivation, and (5) teacher emotional support to anxiety to self-efficacy to intrinsic motivation. Results of mediation analyses revealed that foreign language enjoyment and anxiety independently mediated the relationship between teacher emotional support and intrinsic motivation to learn English. However, self-efficacy did not independently mediate the effect of teacher emotional caring on intrinsic motivation. Further, there was evidence of mediating pathways from teacher emotional support to intrinsic motivation through enjoyment then to self-efficacy as well as anxiety then to self-efficacy. Additionally, when estimating the mediation model, the results are the same whether SEM or an OLS regression is used. The findings of the present research make a contribution to the SLA motivation literature and add additional support for the Self-Determination Theory (SDT). I discuss implications and limitations as well as recommendations for future search.