Figures show that between 2008 and 2012 more than 40% of fatal accidents on single-carriageway sections of the A9 - the main road from the central belt to the Highlands - involved overtaking.
A safety campaign has been launched to raise awareness of road safety issues before the dualling of the route, due to be completed by 2025.
It features a new website giving real-time information on traffic, travel and weather along the 138-mile road, the longest in Scotland.
Transport minister Keith Brown, said: "The issues faced on the A9 are complex and we are adopting a wide range of measures to address these ahead of dualling.
"We are focusing on the three strands of engineering, education and enforcement, and this campaign is the first in a series which will address driver behaviour and help people make better and more informed decisions when they are behind the wheel.
"Road users tell us that they are concerned about the number of dangerous overtaking manoeuvres that they see on the route and the aim of this campaign is to give drivers the knowledge to overtake safely, without putting their lives or those of fellow road users at risk."
Superintendent Iain Murray, head of road policing at Police Scotland, said: "Overtaking is inherently risky and it is imperative that drivers look carefully at the road beyond the vehicle in front and accurately assess the dangers that might exist before attempting to overtake.
"Sadly, this year we have had occasions on the roads in Scotland where overtaking manoeuvres have ended in tragedy, so the simple rule must be 'if in doubt, don't risk it'."
For more information on the campaign, which is backed by the A9 Safety Group, visit www.a9road.info.