Herein,we describe a novel catalytic Pictet-Spengler-type cyclization using CO2 as a nontoxic and sustainable C1 feedstock with environmentally benign and non-precious-metal iron as catalyst.The reaction is achieved by selective four-electron reduction of CO2 into methylene level intermediate through carefully tuning the reaction parameters.A variety of tetrahydro-β-carbolines and other nitrogen-containing heterocycles can be easily obtained under mild conditions.Mechanistic studies have shown that tetrahydro-β-carbolines are probably obtained via spiroindolenine intermediates.