This research paper investigated the effect of consumers' Big Five personality traits on the adoption of residential photovoltaic systems in Germany. To account for different types or groups of households, a multigroup structural equation model with N = 9,281 individuals was analyzed using data from a nationwide, representative household panel. It could be shown that the ways in which personality traits are mediated through environmental concern and risk propensities change depending on whether there is a single household or if additional individuals are involved in the decision-making process. In the aggregated view, direct effects of extraversion could be found for households comprising only a couple. For other households with additional members, no direct effects were found. All five personality traits were mediated by risk preference while openness, agreeableness, and neuroticism were mediated by environmental concern. On the individual level, the examination revealed that the head of household's neuroticism and the partner's openness and extraversion showed significant effects on the purchase of a photovoltaic system - albeit with small effect sizes. The results provide important insights into how household decisions can be better understood in order to contribute to the energy-system transformation.