Computational super-resolution is a novel approach to break the diffraction limit. The Mueller matrix, which contains full-polarization information about the morphology and structure of a sample, can add super-resolution information and be a promising way to further enhance the resolution. Here we proposed a new approach called Mueller-matrix scattered-field microscopy (MSM) that relies on a computational reconstruction strategy to quantitatively determine the geometrical parameters of finite deep sub-wavelength nanostructures. The MSM adopts a high numerical-aperture objective lens to collect a broad range of spatial frequencies of the scattered field of a sample in terms of Mueller-matrix images. A rigorous forward scattering model is established for MSM, which takes into account the vectorial nature of the scattered field when passing through the imaging system and the effect of defocus in the measurement process. The experimental results performed on a series of isolated Si lines have demonstrated that MSM can resolve a feature size of λ/16 with a sub-7 nm accuracy. The MSM is fast and has a great measurement accuracy for nanostructures, which is expected to have a great potential application for future nanotechnology and nanoelectronics manufacturing.