A new method using an atomic-resonance filter and deconvolution techniques has been developed to acquire high-resolution spectra of atmospheric Rayleigh-Mie scattering. In the deconvolution process, the difticulty of the undetermined division 0/0 is overcome by a fitting method. Preliminary laboratory experimental results on 90-deg scattering show that with a signal-to-noise ratio of 20, the scattered Rayleigh-Mie spectrum may be retrieved in agreement with the theoretical analysis.