In this paper, we address the problem of the simultaneous recovery of the shape and refractive index of an object from a spectro-polarimetric image captured from a single view. Here, we focus on the diffuse polarisation process occuring at dielectric surfaces due to subsurface scattering and transmission from the object surface into the air. The diffuse polarisation of the reflection process is modelled by the Fresnel transmission theory. We present a method for estimating the azimuth angle of surface normals from the spectral variation of the phase of polarisation. Moreover, we estimate the zenith angle of surface normals and index of refraction simultaneously in a well-posed optimisation framework. We achieve well-posedness by introducing two additional constraints to the problem, including the surface integrability and the material dispersion equation. This yields an iterative solution which is computationally efficient due to the use of closed-form solutions for both the zenith angle and the refractive index in each iteration. To demonstrate the effectiveness of our approach, we show results of shape recovery and surface rendering for both real-world and synthetic imagery.