A new passive sampler was designed and characterized for the determination of free copper ion (Cu2+) concentration in aqueous solution. Each sampling device was composed of a set of about 30 diffusive milligel (DMG) beads. Milligel beads with incorporated cation exchange resin (Chelex) particles were synthetized using an adapted droplet-based millifluidic process. Beads were assumed to be prolate spheroids, with a diameter of 1.6 mm and an anisotropic factor of 1.4. The milligel was controlled in chemical composition of hydrogel (monomer, cross-linker, initiator and Chelex concentration) and characterized in pore size. Two types of sampling devices were developed containing 7.5% and 15% of Chelex, respectively, and 6 nm pore size. The kinetic curves obtained demonstrated the accumulation of copper in the DMG according to the process described in the literature as absorption (and/or adsorption) and release following the Fick’s first law of diffusion. For their use in water monitoring, the typical physico-chemical characteristics of the samplers, i.e. the mass-transfer coefficient (k(0)) and the samplerwater partition coefficient (K-sw), were determined based on a static exposure design. In order to determine the copper concentration in the samplers after their exposure, a method using DMG bead digestion combined to Inductively Coupled Plasma – Atomic Emission Spectrometry (ICP-AES) analysis was developed and optimized. The DMG devices proved to be capable to absorb free copper ions from an aqueous solution, which could be accurately quantified with a mean recovery of 99% and a repeatability of 7% (mean relative uncertainty).