A monolithic two‐terminal solution‐processed quadruple junction polymer solar cell in an n–i–p (inverted) configuration with four complementary polymer:fullerene active bulk‐heterojunction layers is presented. The subcells possess different optical bandgaps ranging from 1.90 to 1.13 eV. Optical modeling using the transfer matrix formalism enables prediction of the fraction of absorbed photons from sunlight in each subcell and determine the optimal combination of layer thicknesses. The quadruple junction cell features an open‐circuit voltage of 2.45 V and has a power conversion efficiency of 7.6%, only slightly less than the modeled value of 8.2%. The external quantum efficiency spectrum, determined with appropriate light and voltage bias conditions, exhibits in general an excellent agreement with modeled spectrum. The device performance is presently limited by bimolecular recombination, which prevents using thick photoactive layers that could absorb light more efficiently.