The current study aimed to explore alternative motivational profiles of high achievers in Mathematics, within the framework of the Situated Expectancy-Value Theory. Furthermore, it aimed to examine the profiles’ potential differences in relation to self-reported metacognitive processes, such as metacognitive awareness and experiences, and achievement emotions related to Mathematics. A comprehensive evaluation in Mathematics was conducted on a total of 492 ninth-graders, including students from regular junior high schools, experimental junior high schools, and an academically advanced summer program. The assessment involved a battery of school-type mathematical tasks, resulting in the identification of 141 high achievers. Cluster analysis, based on students’ expectancies for success, subjective value, and perceived cost in relation to Mathematics, revealed five motivational profiles labeled as follows: Cluster 1. Higher Motivation, Cluster 2: Higher Expectancies, Value, and Cost, Cluster 3: Lower Expectancies, Cluster 4: Lower Value, and Cluster 5: Lower Motivation. Differences were found among the five profiles in terms of students’ reported metacognitive awareness and their emotions of enjoyment, pride, anxiety, shame, and boredom toward Mathematics. Students with the Higher Motivation profile appeared to be the most adaptive across all of the examined variables, while students with the Lower Motivation profile reported less favorable levels of motivational and affective variables than most others. However, high achievers did not differ significantly regarding their metacognitive accuracy. Examination of the gender distribution within the clusters did not reveal any differences in gender representation.