Bismuth (Bi) has been known as a highly efficient electrocatalyst for CO₂ reduction reaction. Stable free-standing two-dimensional Bi monolayer (Bismuthene) structures have been predicted theoretically, but never realized experimentally. Here, we show the first simple large-scale synthesis of free-standing Bismuthene, to our knowledge, and demonstrate its high electrocatalytic efficiency for formate (HCOO⁻) formation from CO₂ reduction reaction. The catalytic performance is evident by the high Faradaic efficiency (99% at −580 mV vs. Reversible Hydrogen Electrode (RHE)), small onset overpotential (<90 mV) and high durability (no performance decay after 75 h and annealing at 400 °C). Density functional theory calculations show the structure-sensitivity of the CO₂ reduction reaction over Bismuthene and thicker nanosheets, suggesting that selective formation of HCOO⁻ indeed can proceed easily on Bismuthene (111) facet due to the unique compressive strain. This work paves the way for the extensive experimental investigation of Bismuthene in many different fields.