In‐gap states and their effect on recombination rates in quasi‐2D lead–iodide‐based perovskites, intercalated with various spacer molecules, are studied using a combination of scanning tunneling spectroscopy and temperature‐dependent photoconductivity measurements. The results are further analyzed by a Shockley–Read–Hall model. Indications for shallow in‐gap states, positioned at about 0.15–0.2 eV below the bottom of the conduction band, are found. These states are identified as dominating the recombination route of photogenerated carriers in these systems, with a relatively large capture coefficient of about 10−5–10−6 cm3 s−1 at room temperature. First‐principles calculations based on density functional theory imply that these states are not an intrinsic effect of the inclusion of the spacer molecules, but rather one that arises from chemical defect formation or structural deformation of the perovskite layers. The results suggest that further improvement of the performance of solar cells that are based on quasi‐2D perovskites requires, along with enhancing carrier mobility, efforts to suppress the concentration of these detrimental defect states.