Objective methods to assess quantitatively port wine stain (PWS) blanching in response to laser therapy are needed to improve laser therapeutic outcome. Previous studies have attempted to assess objectively PWS color based on point measurement devices. To date, these approaches have typically been limited by a number of factors such as small test area and need for contact. To address these issues, a polarization spectral imaging system and an image analysis method have been developed to evaluate quantitatively erythema and melanin content distribution in skin. The developed polarization spectral imaging system minimizes artifacts such as glaring, shadowing, and non-uniform illumination that interfere with image fidelity. Furthermore, the image analysis method has been employed to get images of skin melanin and erythema indices from the acquired color images for quantitative analysis. Finally, using PWS patient color image, the effectiveness in laser treatment of PWS was evaluated by calculating relative erythema index image that is the relative erythema index of PWS region to the normal region. The developed device and analysis method appears to be a simple and effective method for quantitative analysis of PWS blanching.