Even after adopting various measures, recent years have witnessed a surge in environment‐related issues such as pollution and climate change. These issues have been considered anthropogenic, and it is a well‐received notion that changing human behaviour is crucial for sustainable development. Promoting pro‐environmental behaviour (PEB) requires understanding of associations among relevant factors; the present study aimed to explore the same among a few less‐explored constructs, which, along with other factors, may significantly explain pro‐environmental behaviour. The study examined the direct relationship of PEB with ecological intelligence (EI) and self‐transcendent values. Also, it explored the mediating effects of implementation‐intentions and the moderating effect of the “new ecological paradigm” (NEP) on PEB. The data were obtained from 400 adult participants using a set of standardized questionnaires. The results showed significant direct and indirect associations among EI, self‐transcendent values, implementation‐intentions, the NEP and PEB. Implementation‐intentions significantly mediated the relationship of EI and values with PEB, and the mediation was moderated by the NEP. Individuals low on EI but endorsing the NEP showed implementation‐intentions similar to those with high EI. Knowledge of the interplay among these factors can be utilized to design interventions for promoting PEB.