Instead of using cards, Samsung Pay allows shoppers to use their smartphones to pay for in-store purchases.
Last month, Apple launched its own Apple Pay system in China, also in partnership with UnionPay.
China’s smartphone market, the largest in the world, presents a huge business opportunity for mobile-payment systems.
Apple Pay and Samsung Pay will now compete with Alibaba’s Alipay, which currently dominates China’s electronic payments market.
However, analysts say that mobile payment services provided by Alipay and WeChat were so dominant in China that international newcomers such as Apple and Samsung would face an uphill battle to win market share.
Tencent’s WeChat also has a payment system which is popular in China, and telecommunications giant Huawei launched its own service earlier this month.
Samsung Pay was now available in China on a range of smartphones including the Samsung Galaxy S7, Galaxy S7 edge, Galaxy S6 edge+ and Galaxy Note5, the South Korean electronics giant said.
Samsung said it would have “the opportunity to support additional mid-range models in the future”.
In announcing its official launch, which has been expected since late last year, Samsung said that Samsung Pay currently supports select credit and debit cards of nine major banks in China including China CITIC Bank, China Construction Bank and China Everbright Bank.
The company has previously said it has one critical fact that will in its favor – its technology works with a much larger number of existing payment terminals.
There has been a rapid take-up of smartphones in China, with an estimated 68% of the population now owning one. And digital wallets are becoming a more popular way to pay for goods and services.
Samsung said on March 29 that its payment system was “simple, safe and easy to use” and that it worked “virtually anywhere you can swipe or tap your card in China”.
Unlike Google Wallet and several other earlier payment apps, Samsung says there is no need to unlock its phones to launch a special app to get started.
Like Apple Pay, Samsung Pay will use near field communication technology (NFC), which needs a separate transaction device, but it will also support magnetic secure transmission technology which works on regular credit card machines.
Samsung Pay is currently available in South Korea and the US.
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