The psychological well-being and racial/ethnic identity expression of bilingual multiple-race individuals mixed with Black/African American and another minority racial/ethnic category are largely underrepresented topics in current scholarly literature despite their growing population in the United States. In the current study, the sociohistorical and political processes of colonialism and coloniality were discussed to provide context for the critical examination of familial foreign language ability (FLA), self-esteem (SE), and Black/African American racial/ethnic identity (BRI) expression among multiple-race Black/African American adults (N = 204). Using structural equation modeling, results indicated that higher levels of FLA were related to higher levels of SE. Higher salience and dominance levels of BRI were also related to higher levels of SE among study participants. In addition, higher salience and dominance levels of BRI significantly mediated the relationship between FLA and SE. The importance of acknowledging potential FLA among multiple-race Black/African Americans are also discussed in the context of professional counseling and counselor education. Limitations of the current study and recommendations for future research were also provided.