Incorporating large organic cations to form two‐dimensional (2D) and mixed 2D/3D structures significantly increases the stability of perovskite solar cells. Here, by investigating the initial stages of the crystallization, as well as partially and fully formed perovskites grown using MACl, the origins underlying this favorable alignment are inferred. This mechanism is studied by employing 3‐fluorobenzylammonium in quasi‐2D perovskite solar cells.