Both terminals of a poly(ethylene glycol) (PEG) molecule were terminated with amines. The PEG was electrodeposited onto titanium (Ti) to give it the biofunctions such as blood compatibility. The effects of the amine of PEG terminals and the pH at PEG solution on the adsorption amount of PEG molecules and the thickness of PEG layer immobilized on the Ti surface were evaluated using quartz crystal microbalance technique and X-ray photoelectron spectroscopy. The interfacial reactivity between PEG terminals and the Ti surface was the largest at pH 11, according to the interaction between the charge of terminal amines of PEG and the point of zero charge of Ti oxide. The orientations of PEG molecules immobilized on the Ti surface with immersion or electrodeposition at pH 11 were determined by Fourier transform infrared reflection absorption spectroscopy. Consequently, the terminal amines of PEG were oriented perpendicularly to the surface in electrodeposition rather than in immersion. The charged PEG randomly immobilized on the Ti surface with immersion led to platelet aggregation, whereas U-shaped PEG molecule immobilized with electrodeposition inhibited platelet adhesion and aggregation. The immobilization manners of PEG on the Ti surface were strongly associated with a biofunction such as platelet adhesion.