Pubertal development during early adolescence is modestly associated with individual differences in slowly developing inhibitory control of impulses—an aspect of self-regulation associated with reward-seeking behaviors such as the onset and frequency of sexual activity. However, this effect may be much stronger in resource-poor environments. On the basis of life-history and r/K-selection theories, we tested the hypothesis that early pubertal timing would be more strongly associated with less mature neurocognitive inhibitory control in lower-income environments. In an economically diverse Appalachian sample (N = 157; 138 with complete neuroimaging data) of 14-year-olds (52% male), inhibitory control was measured using the multisource-interference task during functional MRI. Results showed that among poor youths only, more advanced puberty for one’s age was linked with lower inhibitory control for the neural but not the behavioral measure. This finding has implications regarding poverty, neurocognitive development, and health-risk behaviors in adolescence.