The police are said to have arrested a receptionist at the Madison Lodge at TUC in Kumasi after a thumb-printed election 2016 ballot papers were discovered at the hotel.
Following a tip from the New Patriotic Party, police raided the hotel on Monday morning and discovered three bags which contained the ballot papers, according to several social media accounts.
Unconfirmed reports say the individuals were working for the National Democratic Congress (NDC).
Votes appeared to have been cast for President John Mahama of the NDC in at least one of the ballot papers reportedly seized by the police.
The development, which comes just two days before the election, has drawn condemnation from supporters of the NPP on social media who say it is an attempt by the NDC to rig the polls.
The Electoral Commission (EC) has said that the seized ballot papers are not valid for Wednesday's elections because they lack serial numbers.
The NDC has also washed its hands off the matter, asking the police to question the NPP's Asahanti Regional chairman, Bernard Antwi Boasiako "Wontumi", who alerted the police to the ballot papers.
However, the situation is likely to further erode confidence in the government's pledge to ensure free and fair elections.