Countries such as Brazil, Chile and Venezuela will be targeted, as well as other emerging markets such as India, Malaysia and Thailand.
In a scheme of arrangement document circulated to shareholders this week, chairman Sir Nigel Rudd said Pessina and US private equity giant KKR, via their AB Acquisitions vehicle, are 'actively reviewing acquisition opportunities' in markets including Continental Europe, Asia and Latin America.
Expansion will be driven by its healthcare division, which will allow the retailer to test the water for its retail business.
US and European retailers, such as Wal-Mart and Carrefour, have been active in South America for some time. Although regarded as politically unstable, the region offers massive opportunities. Brazil alone is the world's fifth largest economy with a GDP approaching US$800 billion (£400 billion).
PricewaterhouseCoopers chief retail adviser Michael Poynor said: 'European retailers have demonstrated that there is huge potential there. If European retailers can do it, there's no reason why British retailers can't do the same.'
Alliance Boots already operates wholesale networks in 14 countries and 550 pharmacies in the Republic of Ireland, Norway, The Netherlands, Russia, Italy, Thailand and Switzerland. It also has a joint venture in China.
Ernst & Young head of retail Tim Sleep said Boots' international wholesale capability following its merger with Alliance Unichem made developing a retail presence in fast-growing markets easier. 'If you are looking for a market where there is an opportunity for Alliance, there is an opportunity for Boots,' he said.
Sleep said there is a significant trend for UK retailers, which are operating in a market growing at only 2 per cent to 3 per cent, to look to faster-growing markets.
'We are seeing an increased awareness of British brands in emerging markets, where there is a growing middle class and growing disposable income,' he said.
Alliance Boots is likely to examine a 'cluster approach' to countries, for example around retail hotspots such as Singapore, Sleep said.
The scheme of arrangement document also outlined Pessina's plans to 'enhance Alliance Boots' positioning as a leading provider of healthcare and beauty advice and services in the local community' by investing in existing shops and increasing its store count.
AB Acquisitions and Alliance Boots declined to comment on international expansion.