The company behind Ariel, Pantene and Duracell currently racks up more than 200 million kilometres across Western Europe a year by road.
It said it would increase the amount of its goods transported by rail from 10% to 30% by 2015.
The move, which would also lead to cost savings, would cut CO2 emissions by 67,500 tonnes a year and was being rolled out after the success of two pilot projects in Belgium and France, which have been running since July.
Businesses had "no alternative" but to work towards greater sustainability, said Didier Delmotte, P&G product supply operations director of Western Europe, as he announced the plan at the company's plant in Amiens, France, this week. "The pilot schemes have been supplying the UK, France, Belgium and Iberia by train and have proved a huge success.
"Rail is a major opportunity in Western Europe and the collaboration between shipper, container operator and rail provider is key."
P&G was looking to train operators to achieve greater reliability and efficiency, he said, and it hoped it would be able to utilise high-speed railways eventually.
In the current economic climate, there were even greater cost incentives for making operations greener, said global sustainability director Peter White.