The rally called for federalisation and a relevant referendum in the central square of Krasnodon.
Protesters fear that if Kiev’s association agreement goes through and Ukraine's market is completely opened up to Europe, the tougher EU production standards will result in the decline of Ukraine's coal and metallurgy industries and the loss of jobs.
The protesters progressed to the Krasnodonvuhillia Coal Company’s HQ, where they attempted to provoke coal miners who were returning to work to join the protests.
The people who had taken part in a city rally then blocked the office buildings and structural divisions of KCC.
Ukraine’s coal industry has long had close ties with Russia. About three-quarters of people in the neighbouring Donetsk region, one of the country’s largest coal producing states, speak Russian as their native language
Earlier this month the "army of the south-east", a group of armed men who included former riot police, occupied the security service headquarters in Donetsk and demanded a referendum.
The group was greeted by a large crowd including a reported 200 miners, who said they had come to defend the building from a rumoured assault by the authorities.
However, most miners support greater independence from Kiev, according to those involved.
Donbass coalminers were also spotted on the barricades in Kiev before Yanukovych's ousting, showing that not all miners are anti-Kiev.
10% of Ukraine's coal production is sold to Russia, the country's largest trading partner.
Another third goes to power metalworking plants, which also sell most of the final product to Russia.
As Ukraine, gripped by political crisis, has turned towards the rest of Europe, Russia has disrupted trade at the border and orders from Russian companies have ground to a halt.
Rinat Akhmetov, currently Ukraine's richest man, who owns mines across the Luhansk and Donetsk regions, served as a mediator in negotiations between the Donetsk protesters and the Kiev-appointed governor.
It is feared that if the 100,000-plus employees of coalmining enterprises across the states were to rise en masse, it would change the political picture in Ukraine drastically.
It would be a case of history repeating itself mirroring when the Donbass miners' strikes that helped bring about the breakup of the Soviet Union.