Bistability and bifurcation, found in a wide range of biochemical networks, are central to the proper function of living systems. We investigate herein recent model systems that show bistable behavior based on nonenzymatic self‐replication reactions. Such models were used before to investigate catalytic growth, chemical logic operations, and additional processes of self‐organization leading to complexification. By solving for their steady‐state solutions by using various analytical and numerical methods, we analyze how and when these systems yield bistability and bifurcation and discover specific cases and conditions producing bistability. We demonstrate that the onset of bistability requires at least second‐order catalysis and results from a mismatch between the various forward and reverse processes. Our findings may have far‐reaching implications in understanding early evolutionary processes of complexification, emergence, and potentially the origin of life.