The rankings combine international test results and data such as graduation rates between 2006 and 2010.
Sir Michael Barber, Pearson's chief education adviser, says successful countries give teachers a high status and have a "culture" of education.
International comparisons in education have become increasingly significant - and this latest league table is based upon a series of global test results combined with measures of education systems, such as how many people go on to university.
The weightings for the rankings have been produced for Pearson by the Economist Intelligence Unit.
Global competition
The two education superpowers - Finland and South Korea - are followed by three other high-performing Asian education systems - Hong Kong, Japan and Singapore.
The UK - which is considered as a single system, rather than four devolved administrations - is then ranked at the head of an above-average group including the Netherlands, New Zealand, Canada and Ireland.
These are ahead of a middle-ranking group including the United States, Germany and France.
At the lowest end are Mexico, Brazil and Indonesia.
Looking at education systems that succeed, the study concludes that spending is important, but not as much as having a culture that is supportive of learning.
It says that spending is easier to measure, but the more complex impact of a society's attitude to education can make a big difference.
The success of Asian countries in these rankings reflects the high value attached to education and the expectations of parents. This can continue to be a factor when families migrate to other countries, says the report accompanying the rankings.
Looking at the two top countries - Finland and South Korea - the report says that there are many big differences, but the common factor is a shared social belief in the importance of education and its "underlying moral purpose".
Teacher quality
The report also emphasises the importance of high-quality teachers and the need to find ways to recruit the best staff. This might be about status and professional respect as well as levels of pay.
The rankings show that there is no clear link between higher relative pay and higher performance.
And there are direct economic consequences of high and low performing education systems, the study says, particularly in a globalised, skill-based economy.
But there are less straightforward and conflicting messages about how schools are organised.
The ranking for levels of school choice shows that Finland and South Korea have among the lowest levels of school choice. But Singapore, another high performer, has the highest level. The UK is among the upper levels in terms of school choice.
http://www.bbc.co.uk/news/education-20498356
Top 20:
1. Finland
2. South Korea
3. Hong Kong
4. Japan
5. Singapore
6. UK
7. Netherlands
8. New Zealand
9. Switzerland
10. Canada
11. Ireland
12. Denmark
13. Australia
14. Poland
15. Germany
16. Belgium
17. USA
18. Hungary
19. Slovakia
20. Russia
Pearson Rankings Website, including all data and reports: http://thelearningcurve.pearson.com/index/index-ranking