Previous research reports a positive association between possession of mental toughness (MT) and high performance in sportspersons. However, the extent to which MT is related to playing experiences and appreciation of club environment in elite women’s football has received only limited research attention. Accordingly, the present study investigated MT in the context of the English Football Association Women’s Super League (WSL). Specifically, this paper examined relationships between level of MT and external (playing experience, perceptions of club infrastructure, and appreciation of support mechanisms) and internal (self-esteem) factors. A sample of 63 elite female professional football players from the WSL, aged between 18 and 35 years (mean = 25.87,SD= 4.03), completed self-report measures. To objectively validate self-ratings, congruence between self and peer-rated was assessed. This revealed a strong degree of consistency. Subsequent analysis found positive correlations between MT, playing experience (number of years playing football, NoY; and highest level of football achieved, HLA), and External Support. Additionally, Self-Esteem correlated positively with MT, NoY, HLA, and External Support. Moderation analysis found MT interacted with NoY and predicted greater levels of Self-Esteem. Players with lower and mean MT, and more years as a professional were more likely to possess higher Self-Esteem (vs. less years). These outcomes indicated important relationships between MT, External Support, and Self-Esteem. Accordingly, WSL clubs can potentially apply the results of this study to enhance positive player mindset.