Plasma- and water-assisted oxide-oxide thermocompression direct bonding for a self-assembly based multichip-to-wafer (MCtW) 3D integration approach was demonstrated. The bonding yields and bonding strengths of the self-assembled chips obtained by the MCtW direct bonding technology were evaluated. In this study, chemical mechanical polish (CMP)-treated oxide formed by plasma-enhanced chemical vapor deposition (PE-CVD) as a MCtW bonding interface was mainly employed, and in addition, wafer-to-wafer thermocompression direct bonding was also used for comparison. N2 or Ar plasmas were utilized for the surface activation. After plasma activation and the subsequent supplying of water as a self-assembly mediate, the chips with the PE-CVD oxide layer were driven by the liquid surface tension and precisely aligned on the host wafers, and subsequently, they were tightly bonded to the wafers through the MCtW oxide-oxide direct bonding technology. Finally, a mechanism of oxide-oxide direct bonding to support the previous models was discussed using an atmospheric pressure ionization mass spectrometer (APIMS).