The governor told the media that he had accepted Rio's resignation. He, however, requested Rio to continue in office till an alternative arrangement was made.
The newly elected lone Member of he Lok Sabha from Nagaland also submitted his resignation from the 60-member state assembly.
Assembly Speaker Chotisuh Sazo said, "I have accepted his resignation."
While declaring his willingness to contest the parliamentary polls, Rio had said that he wanted to go to New Delhi to play a bigger and important role for the Naga people and the Northeast region.
Rio defeated his closest rival, Congress' KV Pusa by 4,00,225 votes in the recent Lok Sabha polls, which is the second highest winning margin after Narendra Modi's in the country.