Manganese (Mn) is an essential plant nutrient, receiving increased attention due to significant deficiency problems in modern crop production. In aquatic sediments, Mn plays an important role in controlling the mobility of other elements due to its high redox sensitivity. Diffusive gradients in thin films (DGT) is recognized as one of the most promising techniques to assess plant availability of nutrients in soils and mobility in sediments. However, the appropriate conditions where DGT can be used to measure Mn in soils and sediments have not been thoroughly investigated. We deployed DGTs in soil, sediment, and solution to investigate the effect of pH and competition from Ca and Fe ions. We found that by using DGT it is possible to accurately measure Mn in soils at pH levels and Ca and Fe concentrations resembling those of normal and fertile agricultural soils. However, in acid soils at pH below 5.5, Mn measurements might be biased due to potential competition effects caused by Ca. Soil deployments showed that changes in soil redox conditions were closely reflected by the DGT based Mn measurements. This might enable a novel approach of using DGT to predict Mn mobility and plant availability in soils. In reducing aquatic sediments, high concentrations of ferrous ions can displace Mn from the resin-gel of the DGT device. We found this to be a significant problem with longer deployment times.