Satellite-based remote sensing (RS) data are increasingly used to map and monitor local, regional, and global environmental phenomena and processes. Although the availability of RS data has improved significantly, especially in recent years, operational applications to derive value-added information products are still limited by close-range validation and verification deficits. This is mainly due to the gap between standardized and sufficiently available close-range and RS data in type, quality, and quantity. However, to ensure the best possible linkage of close-range and RS data, it makes sense to simultaneously record close-range data in addition to the availability of environmental models. This critical gap is filled by the presented mobile wireless ad hoc sensor network (MWSN) concept, which records sufficient close-range data automatically and in a standardized way, even at local and regional levels. This paper presents a field study conducted as part of the Durable Environmental Multidisciplinary Monitoring Information Network (DEMMIN), focusing on the information gained with respect to estimating the vegetation state with the help of multispectral data by simultaneous observation of an MWSN during a Sentinel-2A (S2A) overflight. Based on a cross-calibration of the two systems, a comparable spectral characteristic of the data sets could be achieved. Building upon this, an analysis of the data regarding the influence of solar altitude, test side topography and land cover, and sub-pixel heterogeneity was accomplished. In particular, variations due to spatial heterogeneity and dynamics in the diurnal cycle show to what extent such complementary measurement systems can improve the data from RS products concerning the vegetation type and atmospheric conditions.