Samsung jumped 24 notches to second place in 2013 from 26th place in 2008, but fell to the No. 3 spot this year.
Another South Korean company LG Electronics moved up eight notches to 17th place, the report said, based on a survey of 1,500 executives of global companies around the world. The annual report is published by the Boston Consulting Group (BCG).
Hyundai Motor and Kia Motors, both South Korean automakers, were ranked 17th and 36th in 2013, respectively, but failed to join the top 50 this year.
Apple Inc. retained the top spot for the 10th consecutive year in 2014, while Google edged out Samsung to be ranked second.
Microsoft was ranked fourth after Samsung.
Also included in the top 10 were IBM, Amazon, Tesla, Toyota, Facebook and Sony.