Reports say the arrests mark an expansion of the probe into what has been called "India's Enron".
Satyam's founder and former chairman, B Ramalinga Raju, is currently in prison awaiting trial after apparently confessing to carrying out the accounting fraud earlier this month.
Speaking to the Financial Times, the inspector-general of police in Hyderabad, VSK Kaumudi, said: "We arrested PwC's chief relationship partner S Gopalakrishnan and engagement leader Srinivas Taluri and are investigating them for fraud and criminal breach of trust."
PwC issued a statement saying it did not know the basis for the pair's arrest but would continue to cooperate with the authorities.
Last week, Satyam's new board announced that they have approached KPMG and Deloitte to restate the company's results. PwC had earlier said that in the wake of Mr Raju's revelations, its results may be "inaccurate and unreliable".