A membrane photobioreactor (MPBR) is a proven and very useful concept in which microalgae can be simultaneously cultivated and pre-harvested. However, the behavior with respect to accumulation of algogenic organic matter, including transparent exopolymeric particles (TEPs), counter ions and unassimilated nutrients due to the recycling of the medium is still unclear, even though the understanding of this behavior is essential for the optimization of microalgae processing. Therefore, the dynamics of these compounds, especially TEPs, during coupled cultivation and harvesting of Chlorella vulgaris in an MPBR with permeate recycle are addressed in this study. Results show that TEPs are secreted during algae cell growth, and that their presence is thus inevitable. In the system with permeate recycle, substances such as counter ions and unassimilated nutrients get accumulated in the system. This was proven to limit the algae growth, together with the occurrence of bioflocculation due to an increasing broth pH.