The U.S. and Europe imposed wide-ranging sanctions against Russia in the wake of its annexation of Crimea from Ukraine in March, with measures including a ban on cooperating on oil exploration in the Arctic as well as targeting politicians, financial institutions, defense technology companies and energy players.
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China has been vocal in opposing the sanctions and Li's three-day official visit, his first since taking office last year, has offered the mainland the chance to scoop up deals which can offset Russia's inability to trade with the West.
But the deals likely won't be on an entirely equal footing.
Russia imports more from China than any other country, but Russia is only China's ninth largest trade partner, just under the U.K., noted Tony Nash, global vice president at Delta Economics.
In addition, Russia may find itself relegated to primarily a supplier for China's factory floors. Indeed, it's a pattern visible in China's trade data for September, with imports unexpectedly rising 7 percent, driven by increasing shipments from commodity-intensive countries, including Russia, which are expected to be processed and re-exported later.
Read More Russia Deputy PM: 'Sanctions not good from any side'
"The Chinese were delighted because it enabled them to get hold of many, many deals that might not have come their way," Colin Chapman, president for New South Wales at the Australian Institute of International Affairs, told CNBC Tuesday, noting that many of the deals expected to be signed during Li's visit are in the energy segment.