Metallic nanoparticles can release ionic species, but also both species can occur in the same samples. Therefore, there is a need of efficient and cost‐effective methods to determine these ionic species in the presence of the corresponding nanoparticles. Electroanalytical techniques open the door to this selective detection of NPs and their ions. In this work, a methodology that allows the direct determination of ionic silver (Ag+) in the presence of silver nanoparticles based on anodic stripping voltammetry was implemented. Silver nanoparticles were determined, after acidic digestion of the sample, by difference with respect to the total content of silver. The method was validated in terms of specific identification of silver ions, linearity, working range, limit of detection, limit of quantification, recovery, repeatability and ruggedness. All parameters are adequate for an analytical method following Eurachem recommendations. The validated method was used to determine the concentration of Ag+ and total silver in two commercial products of colloidal silver. The results were compared with those obtained by atomic absorption spectrometry in combination with an ultrafiltration step for isolation of ionic silver. There were no significant differences in the results. The proposed methodology benefits from the intrinsic selectivity of the electroanalysis methods, allowing to eliminate the steps of pretreatments of the samples, which are necessary in other techniques. The novelty of the article lies in the direct determination of Ag (I) ions in the presence of AgNPs, without the use of previous separation steps.