Progress on changing human behaviour to meet the challenges of regional and global sustainability has been slow. Building on theory as well as small-scale survey and experimental evidence that exposure to nature may be associated with greater pro-environmentalism, the aim of the current study was to quantify relationships between exposure to nature (operationalised as neighbourhood greenspace, coastal proximity, and recreational nature visits) as well as appreciation of the natural world, and self-reported pro-environmental behaviour for the adult population of England. Using data from a nationally representative sample (N = 24,204), and controlling for potential confounders, a structural equation model was used to estimate relationships. Indirect effects of neighbourhood exposures via nature visits and nature appreciation were accounted for. We found positive relationships between both recreational nature visits and nature appreciation and pro-environmental behaviour across both the whole sample and key socio-demographic groups. The more individuals visited nature for recreation and the more they appreciated the natural world, the more pro-environmental behaviour they reported. Although rural and coastal dwellers tended to also be more pro-environmental on average, patterns were complex, potentially reflecting situational constraints and opportunities. Importantly, positive associations between pro-environmental behaviours and high neighbourhood greenspace and coastal proximity were present for both high and low socio-economic status households. Improving access to, and contact with, nature, e.g., through better urban planning, may be one approach for meeting sustainability targets.