No company is obliged to make public the number of employees it has, so there can be no definitive lists.
However simply googling 'major employers xxxxxx', replacing xxxxxx by the name of a county, city or major town might well yield some suitable results. e.g. by googling 'major employers Ipswich' I quickly found this list:
http://www.eadt.co.uk/business/top-100/top-100-table
Joining your local Chamber of Commerce might also prove beneficial with regard to obtaining such information. Membership of the Suffolk Chamber starts at £105 per year.