The paper presents the first part of the work focused on preparation of biodegradable chitosan microcapsules with tailored properties for potential applications in medical field as drug temporary carriers. In this paper, we aimed to prepare chitosan and chondroitin sulphate microcapsules using TPP as the second cross-linker and investigate the formation of the capsule membrane and its permeability in dependence on conditions of polyionic complexation. As a model, TPP was used to assess an influence of concentration and reaction time on the microcapsule formation. The method of inverse SEC was used for pores size and permeability limit of capsules assessment. For chitosan/CHS/TPP capsules, the distribution of pores size in the membrane is rather broad, which can be suitable for applications in tissue engineering and drug delivery systems.