Working with Buying Solutions, the fast-growing Korean car maker will have access to the 100,000-strong fleet of cars used by the likes of the NHS Trust.
The deal highlights the growing trust and popularity of the manufacturer in the UK after a string of new models have wowed the British public.
New models such as the Kia Picanto city car, quirky Kia Soul and stylish Kia Sportage crossover have enabled Kia to grow its market share to record levels in the past 12 months.
Along with the Kia cee’d, which found fame as the car used on Top Gear’s Star in a Reasonably Priced Car section, Kia will offer a range of new cars to customers in the public sector.
John Hargreaves, Head of Fleet and Remarketing at Kia Motors, said: "By working closely with Buying Solutions, Kia will reach a wider fleet audience within the public sector, and will be able to offer corporate fleet loans to sector departments.
"Kia’s participation in the Buying Solutions Framework Agreement is timely as it will give Public Sector fleets the chance to take advantage of our excellent value for money sales proposition."
Kia cars are enjoying a surge in popularity as fleet cars because of the new styling direction at the hands of ex-Audi designer Peter Schreyer and the low prices and running costs of its cars.
For example, both the Kia Picanto and new Kia Rio offer road tax-free levels of CO2 emissions and fuel consumption figures as high as 88mpg.
Larger models such as the Kia Sportage, which offers a four-wheel drive option, delivers 135g/km in its best-performing diesel engine.
This helps the models deliver low rates of CO2-based Benefit-in-Kind tax for UK businesses and high fuel economy figures.
Kia sold 10,000 cars in the first three months of 2011 and currently enjoys a three per cent market share of the UK market.