Sunanda Kotekar, who was deployed at Lodhikheda polling booth in Saunsar area of Chhindwara, felt uneasy on Sunday night, Chief Electoral Officer V L Kantha Rao said.
She died of the heart attack even before she could be provided any medical assistance, he added.
The woman and other personnel of the polling team had reached the booth early on Sunday.
Polling began on Monday morning for elections in the state's six Lok Sabha seats - Sidhi, Shahdol, Jabalpur, Mandla, Balaghat and Chhindwara - and bypoll to Chhindwara Assembly constituency, where Chief Minister Kamal Nath is in the fray.
Chief Minister Kamal Nath cast his vote on Monday in the fourth phase of the staggered Lok Sabha elections in Madhya Pradesh. He cast his vote at polling booth number 17 in Shikarpur, Chhindwara.
Chhindwara is a prestige battle for Kamal Nath who has fielded his son, Nakul Nath, from the seat after winning it nine times. He had won the seat even at the peak of the Modi wave when the Bharatiya Janata Party swept the state in 2014.
Polling began at 7 a.m. for six parliamentary seats and one Assembly bypoll in the state.
Voting is underway in Chhindwara, Balaghat, Jabalpur, Sidhi, Shahdol and Mandla.