A new laboratory-made Zn-ferrite (ZnFe2O4) binding gel is fully tested using DGT (Diffusive Gradient in Thin films) probes to measure total As [including inorganic As(III) and As(V), as well as MMAAV (MonoMethyl Arsenic Acid) and DMAAV (DiMethyl Arsenic Acid)] in river waters and sediment pore waters. The synthesis of the binding gel is easy, cheap and its insertion into the acrylamide gel is not problematic. An important series of triplicate tests have been carried out to validate the use of the Zn-ferrite binding gel in routine for several environmental matrixes studies, in order to test: (i) the effect of pH on the accumulation efficiency of inorganic As species; (ii) the reproducibility of the results; (iii) the accumulation efficiency of As species; (iv) the effects of the ionic strength and possible competitive anions; and (v) the uptake and the elution efficiency of As species after accumulation in the binding gel. All experimental conditions have been reproduced using two other existing binding gels for comparison: ferrihydrite and Metsorb® HMRP 50. We clearly demonstrate that the Zn-ferrite binding gel is at least as good as the two other binding gels, especially for pH values higher than 8. In addition, by taking into consideration the diffusion rates of As(III) and As(V) in the gel, combining the 3-mercaptopropyl [accumulating only As(III)] with the Zn-ferrite binding gels allows for performing speciation studies. An environmental study along the Marque River finally illustrates the ability of the new binding gel to be used for field studies.