Ma Chao was the eldest son of Ma Teng and the brother of Ma Tie and Ma Xiu. Ma Dai was his cousin and servant. His father was a member of the gentry of Liang Province in northwestern China, and was also the sworn brother of Han Sui, another powerful Xiliang regional warlord. In 180 AD, Ma Chao took part in his father's uprising against the brutal military governor Dong Zhuo, and he led the attack on Dong Zhuo's Forces from the front. The battle was a victory for the Allied Forces, who became independent from the evil general. However, in 185 AD, his father sided with the Later Han government when the Qiang rose up, as did Han Sui and Ma Chao, who followed the command of Bian Zhang. Eventually, the Qiang chief Beigong Boyu kidnapped Bian Zhang's family, and forced him to join the rebels. Ma Teng, Ma Chao, Han Sui, and Ma Dai followed Bian Zhang in rebellion, and Ma Chao was one of the soldiers who fought against Sun Jian's army during their suppression of the Liangzhou revolt under Zhang Wen, Huangfu Song, and Geng Bi. They were all defeated, and after Bian Zhang died from illness, the rebellion ended.
When Dong Zhuo was killed by his own general Lu Bu and Minister of the Interior Wang Yun, Ma Teng prepared to attack the capital of Chang'an with 100,000 troops from Xiliang and Bing Province. Ma Chao was one of the generals of his father during his campaign against the capital, held by Li Jue and Guo Si. Ma Yu, Chong Shao, and Liu Fan, the three Han officials that assisted the Xiliang forces from inside the city, were all executed by Li Jue, disheartening the invading army. Ma Chao killed Wang Fang and captured Li Meng, who was executed by the Xiliang forces, but the Xiliang forces were forced to retreat, as they had lost the initiative.
In 202-205 AD, Ma Teng allied with prominent warlord and Han Prime Minister Cao Cao against the remnants of Yuan Shao's Forces and became his vassal. Ma Chao, Ma Dai, and his father's general Pang De were sent to assist Cao Cao in his campaign against Yuan Shang's army in Liyang, and at the Battle of Hedong, Pang De beheaded Yuang Shang's general Guo Yuan in battle. Ma Chao was originally at odds with Cao Cao's strategist Guo Jia, but in the celebrations after the battle, he toasted to Guo Jia along with Ma Dai.
Ma Chao was loyal to Cao Cao until Ma Teng was figured out to have taken part in a conspiracy in 211 AD, laid out by the late Dong Cheng eleven years earlier. Ma Teng was executed with Ma Tie, so Ma Chao, Han Sui, and the Eight Riders of Han Sui formed an alliance in Liang Province against Cao Cao. They captured Chang'an, and Ma Chao declared himself the Governor of Bing Province. However, Ma Chao's army was defeated at the Battle of Tong Gate by Cao Cao's army, and Han Sui defected to Cao Cao. Ma Chao and Ma Dai were forced to flee to Zhang Lu in Hanzhong to flee Cao Cao, who conquered much of his lands. Borrowing troops from Zhang Lu, Ma Chao attempted to regain lost lands, and he became Governor of Bing Province after defeating Cao Cao at the Battle of Ji Castle. However, Cao Cao's armies counterattacked, and he was defeated. Ma Chao later left Zhang Lu's service with his service and headed south to Zhang Lu's rival Liu Zhang, where he fought against Liu Bei, who had invaded Yi Province. At the Battle of Jiameng Gate, he fought Liu Bei's general Zhang Fei, but Li Hui convinced him to surrender to Liu Bei and serve him.
Ma Chao served under Liu Bei against Kebineng of the Xianbei tribe of barbarians, as he was well-versed in barbarian tactics. He fought under him at the Battle of Hanzhong in 219 AD and was sent to guard Hanzhong while Zhuge Liang launched his Nanman Campaign in 225 AD. He died of illness shortly after Zhuge Liang returned, and Zhuge Liang told Zhao Yun that he felt as if he had "lost an arm". His descendant Ma Ying-jeou would be a 21st century President of the Republic of China.