Ramaphosa came to power in February pledging to revive the economy and attract investors after Jacob Zuma was ousted from office at the end of a nine-year reign dominated by graft scandals, low economic growth and record unemployment.
"We have signed several agreements and memorandums of understanding that are intended to further deepen our relations, including investment commitments to the value of $14 billion," Ramaphosa said, standing beside Xi.
"Bilateral trade has not reached its potential," Ramaphosa adding, saying the investment would focus on infrastructure, agriculture and technology.
Xi arrived in South Africa ahead of a summit of BRICS emerging economies -- Brazil, Russia, India, China and South Africa -- starting on Wednesday.
"China... and will take active measures to expand imports from South Africa so as to support the government," Xi said.
Among the deals signed on Tuesday was a $2.5 billion loan to South Africa's state-run power company Eskom, which is burdened by massive debts and embroiled in graft allegations involving Zuma's government.
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