Psychological well-being is a key aspect of mental health. However, it is the focus of few studies among the deaf population. The present study explored the possible relationship between emotional intelligence and psychological well-being in a sample of 146 deaf Spanish adults compared to 146 typically hearing controls. The influence of anxiety, depression, and alexithymia was also assessed. Significant differences were found between deaf and hearing participants regarding anxiety, depression, alexithymia, and psychological well-being. No differences were found between deaf and typically hearing participants regarding emotional functioning. Mediational analysis showed that emotional intelligence significantly predicted psychological well-being both directly, and also indirectly through depression. Effects of anxiety and alexithymia were not significant. Differences observed between deaf and typically hearing participants regarding psychological well-being are discussed in terms of greater depression rates among the former. Deaf participants' intragroup differences are also discussed.