Continuous cultivation of the faba bean will lead to its autotoxicity. Faba bean–wheat intercropping can effectively alleviate the autotoxicity of the faba bean. In order to investigate the autotoxicity of water extracts of various parts of the faba bean, we prepared water extracts of various parts of the faba bean, such as the roots, stems, leaves, and rhizosphere soil. The results showed various parts of the faba bean significantly inhibited the germination of faba bean seeds. The main autotoxins in these parts were analyzed using HPLC. Six autotoxins, namely, p-hydroxybenzoic acid, vanillic acid, salicylic acid, ferulic acid, benzoic acid, and cinnamic acid, were identified. The exogenous addition of these six autotoxins significantly inhibited the germination of faba bean seeds in a concentration-dependent manner. Furthermore, field experiments were conducted to investigate the effects of various levels of nitrogen fertilizer on the autotoxin content and the aboveground dry weight of the faba bean in a faba bean–wheat intercropping system. The application of various levels of nitrogen fertilizer in the faba bean–wheat intercropping system could significantly reduce the content of autotoxins and increase the aboveground dry weight in faba bean, particularly at the N2 level (90 kg/hm2). The above results showed that the water extracts of faba bean roots, stems, leaves, and rhizosphere soil inhibited faba bean seed germination. The autotoxicity in faba bean under continuous cropping could be caused by p-hydroxybenzoic acid, vanillic acid, salicylic acid, ferulic acid, benzoic acid, and cinnamic acid. The autotoxic effects in the faba bean were effectively mitigated by the application of nitrogen fertilizer in a faba bean–wheat intercropping system.