Cs-137 is the most released fission product in the marine environment. It is important to develop a robust in situ technique for its monitoring. The existing diffusive gradients in thin films (DGT) passive sampling techniques for in situ measurement of Cs+ have some limitations due to the ion competition and high pH of seawater. A new DGT sampler based on potassium zinc hexacyanoferrate (KZFCN) as a binding layer has been developed and investigated for the measurement of the time-weighted average concentration of Cs-137 in seawater. This binding layer proved a working pH range of 2–12 and an ionic strength of up to 0.75 M. Two types of diffusive gels were tested and agarose gel (AGE) was chosen for the KZFCN-DGT sampler. The measured Cs+ diffusion coefficient (1.71 × 10–5 cm2·s–1 at 25 °C) in the diffusive gel from seawater was within the expected range published in the literature. The measured concentrations of Cs-137 in seawater obtained by laboratory deployments of the KZFCN-DGT samplers for up to 4 weeks showed good precision (RSD = 13%) and accuracy (relative error = 8.5%) values. The performance test results demonstrated that the KZFCN-DGT sampler is suitable for long-term monitoring of Cs-137 in seawater due to its high capacity and resistance to ion competition and high pH.