Roman said his decision to resign is related to the fact Petroecuador is not in the necessary financial condition to maintain its operations.
Roman also had a falling out with economy and finance minister Diego Borja, local press reported.
Petroecuador has been in a severe financial crisis since 1992 and Borja would not agree to hand over the funds to allow Petroecuador to pay its debts, Roman said.
Roman warned the company will not be able to continue operating if the finance ministry does not respect its autonomy.
"We need US$35mn so that Petroecuador is not paralyzed," he was quoted as saying in a radio interview.
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