The present study contributes to the field of L2 motivation by exploring the link between emotional experience in language learning and motivational self from a multilingual perspective. Specifically, it evaluated the empirical support for the validity of the ideal multilingual self on simultaneous language learners in China and assessed the relationship between emotional experience (positive and negative) in language learning and the ideal multilingual self using structural equation modelling. Five hundred and twenty-three learners of English and languages other than English (LOTEs) in Chinese universities participated in the survey study. Findings established the construct validity of the ideal multilingual self and unveiled the significance and complexity of the link between emotion and motivation. Specifically, learners reported largely similar positive experiences in learning English and LOTEs and positive emotions in both languages were positively linked, with equal magnitude, to the ideal multilingual self. The patterns involving negative emotions were less consistent as learners reported differing negative experiences in learning the two languages and only negative emotion in English learning was negatively linked to the ideal multilingual self. The complexity of patterns brings forth a more nuanced understanding of the connection between emotion and multilingual motivation with pedagogical implications.