Global retrieval of solar induced fluorescence emitted by terrestrial vegetation can provide an unprecedented measure for photosynthetic efficiency. The GOSAT (JAXA, launched Feb. 2009) and OCO‐2 (NASA, to be launched 2013) satellites record high‐resolution spectra in the O2 A‐band region, overlapping part of the chlorophyll fluorescence spectrum. We show that fluorescence cannot be unambiguously discriminated from atmospheric scattering effects using O2 absorption lines. This can cause systematic biases in retrieved scattering parameters (aerosol optical thickness, aerosol height, surface pressure, surface albedo) if fluorescence is neglected. Hence, we demonstrate an efficient alternative fluorescence least‐squares retrieval method based solely on strong Fraunhofer lines in the vicinity of the O2 A‐band, disentangling fluorescence from scattering effects. Not only does the Fraunhofer line fit produce a more accurate estimate of fluorescence emission, but it also allows improved retrievals of atmospheric aerosols from the O2 A‐band.