He was born in Uzyn, Kiev Oblast of Ukrainian SSR to Roman Porfirievich Popovich (a fireman in a sugar factory) and Theodosia Kasyanovna Semyonova. He had two sisters (one older, one younger) and two brothers (both younger).

During World War II, the Germans occupied Uzyn, and burned documents including Popovich's birth certificate. After the war, these were restored through witness testimony, and although his mother knew that he was born in 1929, two witnesses insisted that Popovich was born in 1930, and so this became his official year of birth.

In 1947, he left vocational school in Bila Tserkva with qualifications as a carpenter. In 1951, Popovich graduated as a construction engineer from a technical school in Magnitogorsk, as well as receiving a pilot's degree.

In 1954, he joined the Young Communist League.

He was married to Marina Popovich, a retired Soviet Air Force colonel and test pilot. They had two daughters. They later divorced, and Popovich married Alevtina Oshegova.

Popovich was also a keen weight lifter:

"Service in the Air Force made us strong, both physically and morally. All of us cosmonauts took up sports and PT seriously when we served in the Air Force. I know that Yuri Gagarin was fond of ice hockey. He liked to play goal keeper. Gherman Titov was a gymnastics enthusiast, Andriyan Nikolayev liked skiing, Pavel Popovich went in for weight lifting. I don't think I am wrong when I say that sports became a fixture in the life of the cosmonauts."

He was also a member of the Supreme Soviet of the Ukrainian Soviet Socialist Republic 6th–11th convocations.

After his retirement in 1993, he lived in Moscow.

Popovich died in a hospital in Gurzuf where he had been taken following a stroke on 29 September 2009. Brain hemorrhage was cited as the cause of death. He is buried in Moscow.