The bidirectional reflectance distribution function (BRDF) gives the reflectance of a target as a function of illumination geometry and viewing geometry, hence carries information about the anisotropy of the surface. BRDF is needed in remote sensing for the correction of view and illumination angle effects (for example in image standardization and mosaicing), for deriving albedo, for land cover classification, for cloud detection, for atmospheric correction, and other applications. However, current spaceborne instruments provide sparse angular sampling of BRDF and airborne instruments are limited in the spatial and temporal coverage. To fill the gaps in angular coverage within spatial, spectral and temporal requirements, we propose a new measurement technique: use of small satellites in formation flight, each satellite with a VNIR (visible and near infrared) imaging spectrometer, to make multi-spectral, near-simultaneous measurements of every ground spot in the swath at multiple angles. This paper describes an observing system simulation experiment (OSSE) to evaluate the proposed concept and select the optimal formation architecture that minimizes BRDF uncertainties. The variables of the OSSE are identified; number of satellites, measurement spread in the view zenith and relative azimuth with respect to solar plane, solar zenith angle, BRDF models and wavelength of reflection. Analyzing the sensitivity of BRDF estimation errors to the variables allow simplification of the OSSE, to enable its use to rapidly evaluate formation architectures. A 6-satellite formation is shown to produce lower BRDF estimation errors, purely in terms of angular sampling as evaluated by the OSSE, than a single spacecraft with 9 forward-aft sensors. We demonstrate the ability to use OSSEs to design small satellite formations as complements to flagship mission data. The formations can fill angular sampling gaps and enable better BRDF products than currently possible.