It has been reported that it was selective to produce ammonia on metallic cobalt in the electrocatalytic nitric oxide reduction reaction (eNORR), where hexagonal close-packed (hcp) cobalt outperforms face-centered cubic (fcc) cobalt. However, hydroxylamine is more selectively produced on a cobalt single-atom catalyst (Co-SAC). Herein, we uncover the structural sensitivity over hcp-Co, fcc-Co, and Co-SAC in eNORR by employing a recently developed constant potential simulation method and microkinetic modeling. It was found that the superior activity for ammonia production on hcp-Co can be attributed to its facile electron and proton transfer and a stronger lateral suppression effect from NO* over fcc-Co. The exceptional hydroxylamine selectivity on Co-SAC is due to the modified electronic structure, namely, a positively charged active center. It was found that it is more favorable to produce NOH* over hcp-Co and fcc-Co, while HNO* is more preferable on Co-SAC, which are firmly correlated with the vertical and strong NO adsorption on the former and the moderate adsorption on the latter. In other words, a key factor for selectivity control is the first step of NO* protonation. Therefore, the local structure and electronic structure of the catalysts can be critical in regulating the activity and selectivity in eNORR.