Government spokesman Nattawut Sai-Kau said National Police Chief Gen. Pacharawat Wongsuwan has been moved to an inactive post in the prime minister's office.
Nattawut declined to comment on the order, issued by Prime Minister Somchai Wongsawat.
It was not clear if Pacharawat was removed because the police failed to evict the protesters, but it could be because he apparently made no attempt to negotiate a peaceful end to the crisis, as the government had asked.
Interior Minister Kowit Wattana met with police at a precinct near Suvarnabhumi on Friday.
About 200 police, carrying riot gears and shields, were seen outside airport offices, which are about 400 yards (meters) from the terminal where the protesters are camped out.
The airport takeover capped months of demonstrations by the protesters, who belong to the People's Alliance for Democracy. They took over the prime minister's office three months ago, virtually paralyzing the government.
They say they won't give up until the government steps down.
"We are ready to defend ourselves against any government's operations to get us out of those places," said Parnthep Wongpuapan, an alliance spokesman.