A total of nine officers have been called in to court by anti-corruption prosecutors to answer questions about their connections with the mafia ring headed up by kingpin Gao Ping.
The agents are facing possible charges of corruption, bribery and revealing classified information, Spain's Cadena Ser radio station reported on Tuesday.
The bribes involved are believed to include legs of ham, bottles of wine and tickets to bullfights and Real Madrid football games.
But two officers on Tuesday denied the charges. Other officers are set to appear in coming days.
Among those suspects still to appear is Carlos Salamanca, police commissioner at Madrid's Barajas Airport. Salamanca is described as having an "extraordinarily close friendship" with mafia member YongPing Wu Liu, according to a police internal affairs report.
One one occasion, the commissioner stopped the repatriation of a Chinese woman in exchange for a leg of ham and case of wine, the report alleges.
The wife of another officer reportedly received a trip to China from Gao Ping after her husband helped a Chinese citizen obtain Spanish documents.
The police officers' appearance is the latest episode in a long-running investigation into the mafia organization established by Gao Ping.
Gao Ping, currently in prison, was arrested in October 2012 along with dozens of mostly Chinese suspects as part of a police investigation dubbed 'Operation Emperor'. He is currently being held without bail.
Spanish prosecutors suspect Gao of leading a gang that allegedly laundered up to €300,000 ($392,000) a year, dodged taxes, bribed officials and forged documents.
Gao, reportedly from Zhejiang in northeastern China, owns art galleries in Madrid and Beijing plus businesses in Cobo Calleja, a huge Chinese trading estate in southern Madrid.
Judges are due to decide at an unspecified date whether he will go on trial.
Police seized €10 million in cash as part of their operation as well as 200 cars, several guns, jewels and art works.
Gao's lawyer, Jaime Sanz de Bremond, on Tuesday accused Spain's anti-corruption prosecutor of "manipulation" and a "lack of rigour".
He said his client had never had any contact with Carlos Salamanca but knew some of the other officers involved because his children went to the same school.