•The paper elaborates an empirical analysis of the relationships between ICTs, digital skills and green diversification in European regions.•The econometric analysis is on a panel of 142 regions (NUTS-1 and NUTS-2), in 22 European countries, for the period 2006-2013.•The level of e-skills in the workforce is a positive predictor of regions’ ability to specialise in new technological domains, and this effect is stronger for green than non-green specializations.•Also, e-skills negatively moderate the effect of relatedness on technological diversification. This negative moderation holds for both green and non-green diversification.•The study brings together two core dimensions of the current EU agenda – digitalisation and transition towards sustainability – and, in so doing, opens up new avenues for the debate of Smart Specialization Policies. Prior research identifies relatedness as a key driver of new specializations in the domain of green technologies. The present paper extends the evolutionary economic geography framework by focussing on digital literacy. Specifically, we argue that workforce skills associated with the use and development of ICT technologies are an important, if understudied, determinant of regional diversification into new green technologies. Accordingly, we analyse their relationships with relatedness and green diversification using panel data on 142 European regions for the period 2006 – 2013. We find that e-skills endowment is a positive predictor of regions’ ability to specialise in new technological domains, and especially for green specializations. Further, e-skills negatively moderate the effect of relatedness on technological diversification. These results call attention to the potential of digitalisation in the context of the transition towards a greener economy.