The development of N2 reduction reaction (NRR) electrocatalysts with excellent activity and selectivity is of great significance, but adsorption-energy linear scaling relations between reaction intermediates severely hamper the realization of this aspiration. Here, we propose an elegant strain engineering strategy to break the linear relations in NRR to promote catalytic activity and selectivity. Our results show that the N–N bond lengths of adsorbed N2 with side-on and end-on configurations exhibit opposite variations under strains, which is illuminated by establishing two different N2 activation mechanisms of “P-P” (Pull-Pull) and “E-E” (Electron-Electron). Then, we highlight that strain engineering can break the linear scaling relations in NRR, selectively optimizing the adsorption of key NH2NH2** and NH2* intermediates to realize a lower limiting potential (UL). Particularly, the catalytic activity-selectivity trade-off of NRR on MXene can be circumvented, resulting in a low UL of −0.25 V and high Faraday efficiency (FE), which is further elucidated to originate from the strain-modulated electronic structures. Last but not least, the catalytic sustainability of MXene under strain has been guaranteed. This work not only provides fundamental insights into the strain effect on catalysis but also pioneers a new avenue toward the rational design of superior NRR catalysts.