The main goal of the present study was to identify and validate latent classes of suicidal behavior in a representative sample of adolescents. The sample comprised a total of 1506 students, including 667 males (44.3%), selected through a sample stratified by clusters. The mean age was 16.15 years (SD = 1.36). The instruments used evaluated suicidal behavior, positive and negative affect, emotional and behavioral problems, prosocial behavior, and subjective well-being. Using the Paykel Suicide Scale, the latent class analysis identified four homogeneous subgroups: “low risk”, “suicidal act”, “suicidal ideation”, and “high risk for suicide”. These subgroups presented a differential pattern in terms of their social-emotional adjustment. The subgroups with the highest theoretical risk showed lower scores on subjective well-being and positive affect as well as higher scores on emotional and behavioral problems and negative affect compared to the non-risk subgroups. This study contributes to an understanding of the typologies of suicidal behavior among adolescents and the relationship with psychopathological adjustment. Ultimately, these findings may promote the development or improvement of early detection and prevention strategies in the suicidal behavior field in order to reduce the socio-economic burdens associated with suicide in young populations.