The unpaid invoices originated with dozens of little-known companies acting as middlemen for Venezuela's oil exports since U.S. sanctions in 2020 halted deals with international trading firms and customers.
Venezuela's Attorney General's office in October began a probe after oil tankers absconded without full payment to PDVSA.
Venezuela's oil ministry and PDVSA did not reply to a request for comment.
Maroil boosted Venezuela's petcoke exports following a commercial pact with PDVSA in 2016.
In Venezuela, two heavy oil upgrading facilities controlled by PDVSA, Petro San Felix and Petrocedeno, produce and store petcoke.