The highway passed through the cities of Surat, Dhule, Jalgaon, Bhusaval, Khamgaon, Akola, Amravati, Nagpur, Bhandara, Rajnandgaon, Durg, Raipur, Mahasamund, Bargarh, Sambalpur, Kharagpur, Kolkata.

It is still known as Old Kolkata-Mumbai Road prior to 1999 period & it used to go via Kharagpur, Jhargram, Chilkigarh, Chichra, Gopiballavpur, Kandnashol, Murgabadi, near Baripada, Bhajpur Chowk in Bhanjpur, Gangraj, Kalabadia, Pathuri to Bangriposi.

Many cities and towns in various districts in the States of Gujarat, Maharashtra, Chhattisgarh, Odisha, Jharkhand and West Bengal were connected by National Highway 6.

Deogarh - Balam - Barkote To shorten distance of National Highway 6, 4 lane wide Tatanagar - Rourkela Expressway is planned.

The Tatanagar - Rourkela Expressway will increase Kolkata to Sambalpur distance to 631 kilometres (392 mi), but will reduce 1 hour 15 minute travel time.