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Two robbers - wearing scarves over their faces and dressed as litter pickers - tied up store workers and emptied a safe of around £11,000.
The men were said to be wearing high visibility jackets and carrying litter spikes when they raided the One Stop shop on Watling Street in Chatham at 6am today.
They tied up two staff members, before fleeing with thousands in a black sack.
DS Heather Thompson said: "This was no doubt a distressing incident for the staff involved and fortunately they were uninjured.
"Officers are carrying out enquires and I would ask that witnesses or anyone with information gets in touch.
"The incident happened early in the morning, but it is likely there were dog walkers, joggers or commuters in the area.
"I would encourage anyone who saw two people matching the descriptions of the suspects or anyone acting suspiciously in the area around the time of the incident to contact police."
Anyone with information is urged to contact DS Thompson on 01634 792555, and quoting XY/18851/14.
Alternatively, contact Kent Crimestoppers anonymously on 0800 555 111.