They were equipped with bogies having two gear ratios, similar to those of the BB9400 with a D.C. generator feeding Pielstick 16 Pa traction motors. The first units were delivered in 1963 to the depots at Chambéry and Nîmes where they ousted steam on the right bank of the Rhône and in the Alps. They then ran with the addition of a boiler van (fourgon chaudiere C922) in order to steam-heat their passenger coaches and also hauled freight trains working in multiple. Gradually spreading across the network, further locos were sent to Rennes, Caen and Clermont-Ferrand.

In 1969, technical advances brought about the BB67300's, derived directly from the BB67000 but equipped with an alternator allowing electric train heating and power supply. The same year, the BB 67400 and CC 72000's gradually took over from the BB 67000's which lost express train haulage and were relegated to freight work. The usefulness of the BB67000 was worsening during the 1970's and it was decided to modify a number of locos to BB67300. The latter kept the same body, but were fitted with an alternator. Finally after the arrival of the South-eastern TGV, the SNCF decided to build the BB67200 class which were equipped with TVM300 cab signalling which allowed them to operate on the high speed lines. The installation of an auto coupler also enabled them to rescue failed TGV 's. About sixty locos were thus modified over the period up to 1996. The rest of the BB 67000 fleet, limited to 90 km/h was then based at Avignon depot and could be seen hauling freight trains in the Bouches du Rhône area. These locos were also used on construction trains on the high speed lines, their last duties being on the Mediterranean LGV.