A new method is presented for the extraction of the complex index of refraction from the extinction efficiency, $$Q_{ext} {({\tilde{\nu }})}$$ Q ext ( ν ~ ) , of homogeneous and layered dielectric spheres that simultaneously removes scattering effects and corrects measured extinction spectra for systematic experimental errors such as baseline shifts, tilts, curvature, and scaling. No reference spectrum is required and fit functions may be used that automatically satisfy the Kramers–Kronig relations. Thus, the method yields the complex refractive index of a sample for unambiguous interpretation of the chemical information of the sample. In the case of homogeneous spheres, the method also determines the radius of the sphere. In the case of layered spheres, the method determines the substances within each layer. Only a single-element detector is required. Using numerically computed $$Q_{ext}({\tilde{\nu }})$$ Q ext ( ν ~ ) data of polymethyl-methacrylate and polystyrene homogeneous and layered spheres, we show that the new reconstruction algorithm is accurate and reliable. Reconstructing the complex refractive index from a published, experimentally measured raw absorbance spectrum shows that the new method simultaneously corrects spectra for scattering effects and, given shape information, corrects raw spectra for systematic errors that result in spectral distortions such as baseline shifts, tilts, curvature, and scaling.