Although many colloidal assembling systems have been reported, most systems suffer from severe aggregation under high solid concentrations, which can often be observed in typical hetero-aggregation system. In this study, we created a hetero-assembly system using concentrated (similar to 50 vol%) suspensions by mixing large SiO2 particles modified with polyacrylic acid partially complexed with oleylamine (PAA-OAm) and small SiO2 particles modified with polyethyleneimine partially complexed with oleic acid (PEI-OA) in a non-aqueous solvent. We demonstrated that hetero-assembly is driven by the interactions between the uncomplexed carboxyl/amine groups of the PAA/PEI present on the particles, while severe aggregation is simultaneously prevented by the steric repulsions of the aliphatic oleyl chains. Comparison of the cross sections of the in-situ solidified hetero-assembled suspensions with those of ideally assembled structures which were reproduced by a simulation considering the statistical distribution of particles strongly supported successful particle assembling via the proposed approach. The results revealed that the OA content in the PEI-OA complex was the dominant factor that controlled the dispersion and assembling state of the binary particles. The significance of this study is that our findings will provide a class of colloidal dispersion state which binary particles were assembled in a high solid content suspension without forming strong aggregates. (C) 2019 The Society of Powder Technology Japan. Published by Elsevier B.V. and The Society of Powder Technology Japan. All rights reserved.