Emotions play an integral role in learning. It is an effective response to a stimulus which can be experienced felt along a positive-negative continuum. Achievement emotions arise from academic activities, and can activate or de-activate educational motivation responses. Based on Control Value Theory, this study examined how negative achievement emotions impact high school students' decision to pursue tertiary education, and what were the contributing factors of these emotions. One thousand five hundred and forty-seven high school students participated in the survey, and data were solicited via established inventories as well as an open ended question. Quantitatively, Partial Least Squares structural equation modelling found boredom and test anxiety to significantly lower students' decision to pursue tertiary education. The precursors to negative achievement emotions stem from examinations and assessments, struggle in lessons, learning itself, parental expectations to excel, and mental health issues. Findings demonstrated the potential of emotions in influencing students' value orientation with respect to tertiary education. As the study is based on a post-pandemic context, implications of findings are discussed in view of the underlying post-pandemic challenges accompanied by recommendation to stakeholders.