Asda chief operating officer David Cheesewright, Morrison chairman Sir Ken Morrison, Sainsbury's chief executive Justin King and Tesco company secretary Lucy Neville-Rolfe all attended the meeting at the Department for Environment, Food and Rural Affairs (Defra).
Miliband asked the retailers how they could meet Government targets for cutting carbon emissions and reducing food miles by increasing their uptake of locally produced seasonal food.
The environment secretary also called for the big chains to improve labelling on electrical goods, making it clear to customers how green the products are.
Retailers have been keen to advertise their environmentally friendly policies over recent months.
Tesco has invested in purpose-built green trains to transport goods from the Midlands up to Scotland. Earlier this year, it launched a 10 point community plan, earmarking£100 million to fund wind turbines, solar panels and geo-thermal power sources for its stores.
Asda has used freight trains to carry goods for more than four years and is working on several initiatives, including bio-diesel and double-tier lorries, to improve its fleet transport.
All of the major supermarkets have pledged to increase their use of local suppliers wherever possible.