Scottish Secretary Michael Forsyth said that devolution and a Scottish parliament with tax-raising powers would cost jobs and damage inward investment.
The campaign will be fought on 100 billboards in Scottish towns and cities. The first two posters were unveiled on a hoarding in Edinburgh, across the street from the offices of the Liberal Democrats, Labour's partners in the Scottish Constitutional Convention.
One of the blue and white posters asks: 'As jobs go south - will you still have yours?' The other suggests that the United Kingdom means 'new jobs', while the tartan tax means 'nae jobs'.
In addition to attacking Labour and Liberal Democrat tax proposals, Mr Forsyth questioned the effect of a reduced number of Scottish MPs at Westminster and the loss of the post of Scottish Secretary.