Previous explanations regarding transnational solidarity in the European Union (EU) have mainly focussed on factors including left–right self‐placement, support for European integration and European identity. We expand this model by considering deeper psychological determinants of transnational solidarity: values, operationalised as Schwartz's basic human values of universalism and security. We expect them to exert (1) direct effects on transnational solidarity – measured as support for pan‐European social benefits – and (2) indirect effects via the three aforementioned factors. We test and find evidence to support our theoretical framework using multigroup structural equation modelling and data from the European Social Survey. We further show that the effect size of the value of universalism on preferences for an EU social benefit scheme in each country is positively moderated by that country's net contribution to the EU budget, highlighting the interaction between material interests and psychological value motivations.