Deals signed covered areas including exports and shipbuilding. China also showed an interest in buying railways and building an airport in Crete.
China is eager to take a majority stake in the Piraeus port. A Chinese company already runs two piers at the port.
Greece is keen to attract foreign investment to reduce its national debt and high unemployment rate.
Li Keqiang has been in Greece as part of a tour of European countries. It is his first visit there since he took office in 2013.
“China attaches great importance to Greece’s unique geographic advantage of being a gateway to Europe,” the two countries said earlier in a joint statement.
Greek PM Antonis Samaras said China was interested in Greece’s airports, and he hoped the country could “become a transit hub for air transport”.
Li Keqiang described the port of Piraeus as “a pearl in the Mediterranean Sea” and said it could become “one of the most competitive ports of the world”.
China’s state-run shipping company, Cosco, won a 35-year lease to expand two main container terminals at the port in 2008.
It also wants to invest $310 millio in expanding the port, in a deal that would require European Union approval.
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