Živojinović was born in the village of Koraćica under the Kosmaj mountain, near Mladenovac, Serbia (then Kingdom of Yugoslavia). After graduating from acting schools in Niš and Novi Sad, he enrolled at the Drama Academy in Belgrade. Velimir Živojinović preferred acting in theatre to acting on screen, and made his screen debut in 1955 film Pesma sa Kumbare was the beginning of an incredibly prolific silver screen career. Bata Živojinović's played both heroes and villains and switched between leading and supporting roles. The zenith of his popularity came with WW2-themed action films in the 1970s. One of his best known films from that period was Valter brani Sarajevo (English translation: Walter Defends Sarajevo), which gained major success in China. He was also known for his close friendship with the Croatian actor Boris Dvornik. In 1991 Živojinović and Dvornik renounced each other in a series of open letters, which was a gesture often seen as symbolic of the breakup of Yugoslavia. In 2004 it was reported that the two men tried to reconcile. In 2006, the two men publicly reconciled on TV via a video link between Split and Belgrade. The actor said that "In the last few years there hasn't been hatred between us", and Dvornik completed the sentence "only a misunderstanding". In 1990 he was elected for the Serbian Parliament, as a member of Slobodan Milošević's Socialist Party of Serbia.Živojinović was awarded Golden Arena for Best Actor at the Pula Film Festival three times: in 1965, 1967 and 1972. He won the award for Best Actor at the 11th Moscow International Film Festival in 1979 for his role in Moment. In 1981 he was a member of the jury at the 12th Moscow International Film Festival. In August 1993, he was awarded Life Achievement Award "Slavica"
Živojinović had a heart attack in October 2006 and suffered from gangrene in his right foot for about three years afterwards. Doctors initially wanted to amputate the limb, but he traveled to Cuba, where his daughter lives, and within the 25 days that he spent being treated there, was cured of the gangrene by Doctor Montekin, who has also treated Venezuelan President Hugo Chavez. The heart attack greatly damaged his heart, and his blood vessels are in poor condition, adding to his many health problems such as diabetes. His heart was operated on twice: first to expand his arteries, then for a double bypass. On 3 July 2012 he suffered a severe stroke and was transported to a hospital specializing in cerebrovascular diseases called Sveti Sava in Belgrade. He was treated in the intensive care unit and was reported to be in critical condition. Reports also stated that after the stroke he was in a coma for two days. After waking up, although not fully lucid, was talking a little.He remained in critical condition in the hospital for about three weeks and had experienced bleeding and weight loss. After treatment for the stroke, he was reported to not be able to walk without assistance and that it was difficult for him to speak. Bata and his doctors remained optimistic that he would make a full recovery with a little more treatment, both in the hospital and after he is discharged.