The local government accountant, Ali Lawan Dachia, was also shot dead.
One other soldier and a policeman were killed in the attack.
Yobe Police Commissioner Patrick Egbuniwe said the incident occurred about 5:40pm.
Sources said the salary of the workers is over N35 million.
The vehicle was conveying the salary from Gashua Local Government and was ambushed at the entrance to Gulani.
Snatching of council workers’ salary has become a common occurrence in the state.
In April, a team of gunmen snatched the salary of workers of Potiskum Local Government while payment was going on. In July, gunmen stole the salary of primary school teachers in Gujba Local Government.
In neighbouring Borno State, gunmen killed a policeman and three council workers before stealing the salary of Shani Local Government workers in July. In June, two soldiers and the cashier of Guzamala Local Government were killed. The salary of the workers was stolen.
The stealing of workers’ salary also occurred in Jere and Kala-Balge local governments earlier in the year.