Surface reflectance measurement is an integral part of the vicarious calibration of satellite sensors and the validation of satellite-derived top-of-atmosphere (TOA) and surface reflectance products. A well-known practice for estimating surface reflectance is to conduct a field campaign with a spectrometer and a calibration panel, which is labor-intensive and expensive. To address this issue, the Radiometric Calibration Network, RadCalNet, has been developed, which automatically collects surface reflectance over several selected sites. Neither of these approaches can continuously track the atmosphere, which limits their ability to compensate for atmospheric transmittance change during target measurement. This paper presents the dual-spectrometer approach that uses a stationary spectrometer dedicated to continuously tracking changes in atmospheric transmittance by staring at a calibrated reference panel while the mobile spectrometer measures the target. Simultaneous measurement of the reflectance panel and target help to transfer calibration from the stationary spectrometer to the mobile spectrometer and synchronize the measurements. In this manner, atmospheric transmittance changes during target measurement can be tracked and used to reduce the variability of the target surface reflectance. This paper uses field measurement data from combined field campaigns between different calibration groups at Brookings, South Dakota, and Landsat 8 and Landsat 9 underfly efforts over Coconino National Forest, Arizona, and Guymon, Oklahoma. Preliminary results show that even in a clear sky condition, where atmospheric transmittance changes are minimal, the precision of target surface reflectance estimated using the dual-spectrometer approach is 2–6% better than the single-spectrometer approach. The dual-spectrometer approach shows the potential for a substantial improvement in the precision of the target spectral profile when the atmospheric transmittance is changing rapidly during field measurement. Results show that during non-optimal atmospheric conditions, the dual-spectrometer approach improved the precision of the surface reflectance by 50–60% compared to the single-spectrometer approach across most spectral regions. The ability to estimate surface reflectance more precisely using the dual-spectrometer approach in different atmospheric conditions improves the vicarious calibration of optical satellite sensors and the validation of both TOA and surface reflectance products.