Metal halide perovskites have achieved photovoltaic efficiencies exceeding 22%, but their widespread use is hindered by their instability in the presence of water and oxygen. To bolster stability, researchers have developed low-dimensional perovskites wherein bulky organic ligands terminate the perovskite lattice, forming quantum wells (QWs) that are protected by the organic layers. In thin films, the width of these QWs exhibits a distribution that results in a spread of bandgaps in the material arising due to varying degrees of quantum confinement across the population. Means to achieve refined control over this QW width distribution, and to examine and understand its influence on I. photovoltaic performance, are therefore of intense interest. Here we show that moving to the ligand allylammonium enables a narrower distribution of QW widths, creating a flattened energy landscape that leads to x1.4 and X1.9 longer diffusion lengths for electrons and holes, respectively. We attribute this to reduced ultrafast shallow hole trapping that originates from the most strongly confined QWs. We observe an increased PCE of 14.4% for allylammonium-based perovskite QW photovoltaics, compared to 11-12% PCEs obtained for analogous devices using phenethylammonium and butylammonium ligands. We then optimize the devices using mixed-cation strategies, achieving 16.5% PCE for allylammonium devices. The devices retain 90% of their initial PCEs after >650 h when stored under ambient atmospheric conditions.