At least a quarter of road deaths involve a person driving for work, according to road safety charity Brake.
People who drive for work are being urged to consider road safety
It said Department for Transport (DfT) figures showed 26% of deaths on Britain's roads last year - 858 out of 3,172 - involved at-work drivers.
Jools Townsend, head of education at Brake, urged businesses to "reduce risks" to employees who drive for work.
The DfT said it was determined to reduce the number of deaths involving those driving for work.
A spokesman said the first safety campaign aimed predominantly at work-related drivers had been launched.
He said the "Think! Driving for Work campaigned" was "aimed predominantly at van drivers and highlighted the real dangers that arise from distractions - such as eating and drinking, reading maps or talking on a hands-free phone while driving".
Brake said the actual figure for work-related driving deaths could be much higher, with indications that these casualties were being under-reported by police.
The charity said DfT figures for accidents last year show an increase of 9% in deaths and serious injuries in crashes involving at-work drivers from 2005.
Ms Townsend said: "It's shocking that so many people are killed or hurt due to at-work driver crashes - and the reality could be even worse than these statistics suggest."
She went on: "We're urging businesses to wake up to the need to manage and reduce risks faced by employees driving for work - and the risks posed to others.
"That means having a comprehensive safe driving policy, to ensure drivers are not under pressure to take risks like speeding or driving when tired, and educating drivers on the consequences of breaking rules behind the wheel."
The DfT spokesman said the next phase of its work-related driving safety campaign would be launched in March and would also address company car drivers.
He said: "We are also working directly with businesses to help them keep their employees safe on the road.
"Employers and employees alike need to realise that there are more effective ways of getting the job done than by risking lives."