A improved spectral reflectance reconstruction method is developed to transform camera RGB to spectral reflectance for skin images. Rather than using conventional direct or two-step processes, we transform camera RGB to skin reflectance directly using a principal component analysis (PCA) approach. The novelty in our direct method (RGB to spectra) is the use of a skin-specific colour characterisation chart with spectra closer to human skin spectra, and a new database of skin reflectances to derive the PCA bases. The experimental results using the facial images of 17 subjects demonstrate that our new direct method gives a significantly better performance than conventional, two-step methods and direct methods with traditional characterization charts. This new spectral reconstruction algorithm is sufficiently precise to reconstruct spectral properites relating to chromophores and its performance is within the acceptable range for maxillofacial soft tissue prostheses (error < 3 ΔE*ab units).