Nanoparticles (NPs) in the environment can interact with macromolecules in the surrounding environment to form eco-corona on their surfaces, which in turn affects the environmental fate and toxicity of nanoparticles. Wastewater treatment plants containing large amounts of microbial extracellular polymeric substances (EPS) are an important source of NPs into the environment, where the formation of EPS coronas on NPs is critical. However, it remains unclear how the crystalline phase and exposed facets, which are intrinsic properties of NPs, affect the formation of EPS coronas on NPs. This study investigated the formation of EPS corona on three TiO NPs (representing the most widely used engineered NPs) with different crystalline phases and exposed facets. The protein type and abundance in EPS coronas on TiO NPs varied depending on the crystalline phase and exposed facets. Anatase with {101} facets and {001} facets preferred to adsorb proteins with lower molecular weights and higher H-bonding relevant amino acids, respectively, while EPS corona on rutile with {110} facets had proteins with higher hydrophobicity. In addition, the selective adsorption of proteins was primarily determined by steric hindrance, hydrogen bonding, and hydrophobic interaction between TiO NPs and proteins, which were affected by changes in aggregation state, surface hydroxyl density, and hydrophobicity of TiO NPs induced by crystalline phase and exposed facets. Moreover, crystalline phase and exposed facets-induced EPS corona changes altered the aggregation state and oxidation potential of TiO-EPS corona complexes. These findings emphasize the important role of crystalline phase and exposed facets in the environmental behavior of nanoparticles and may provide insights into the safe design of nanoparticles.