This work explores the connection between psychological well-being and Internet use in older adults. The study is based on a sample of 2314 participants in the English Longitudinal Study of Aging. The subjects, aged 50 years and older, were interviewed every two years over the 2006–2007 to 2014–2015 period. The connection between the use of Internet/Email and the main dimensions of psychological well-being (evaluative, hedonic and eudaimonic) was analyzed by means of three generalized estimating equation models that were fitted on 2-year lagged repeated measurements. The outcome variables, the scores on three well-being scales, were explained in terms of Internet/Email use, controlling for covariates that included health and socioeconomic indicators. The results support the existence of a direct relationship between Internet/Email use and psychological well-being. The connection between the main predictor and the score of the participants on the scale used to measure the eudaimonic aspect was positive and statistically significant at conventional levels (p-value: 0.015). However, the relevance of digital literacy on the evaluative and the hedonic components could not be confirmed (p-values for evaluative and hedonic dimensions were 0.078 and 0.192, respectively).