Firefighters extricated the Mernda man from the large B-double truck before he was transported to hospital for observation.
A mop up operation continues with FRV Hazmat crews working to clean up the chemical pesticide that spilt onto the road from the truck.
An exclusion zone is in place for residents in Tullamarine, who have been warned to avoid the area and urging people to stay indoors.
The warning was issued for Airport West, Gladstone Park, Gowanbrae, Strathmore Heights and Tullamarine.
The clean-up effort is expected to take most of the day.
Victoria Police are assisting with traffic management at the scene, while the Melrose Drive exit from the M80 Ring Road Altona-bound is closed due to the rollover.
Drivers are advised to allow for extra time and use alternative exits onto the Tullamarine Freeway or Airport Drive.
The circumstances surrounding the crash are yet to be determined.
Anyone with dashcam footage is urged to contact Crime Stoppers on 1800 333 000.
Join Tom Tilley with regular rotating co-hosts Jan Fran, Annika Smethurst and Jamila Rizvi on The Briefing, Monday - Saturday, for the day's headlines and breaking news as well as hot topics and interviews. Available on Listnr.