Internal Government emails also show strenuous efforts were made by officials to counter claims of a possible conflict of interest arising from Lena Wilson's dual role.
The Herald revealed her appointment to FTSE-100 safety services firm Intertek on June 12. Ms Wilson joined the board of the London-based firm in a "personal capacity" on a salary of £55,000 for one day's work per month.
The appointment was endorsed by SE chairman Crawford Gillies but critics demanded an inquiry, claiming she should focus on her £200,000 role as chief executive of the taxpayer-funded economic development agency.
Documents released under Freedom of Information show Finance Secretary John Swinney discussed the move personally with Mr Gillies before the announcement was made.
At 7.02am on June 11, an official at SE – whose name has not been made public – emailed senior Government officials to let them know a statement by Intertek was imminent.
He included a copy of the press release due to be issued and added: "I know Crawford has been speaking to Mr Swinney on this directly."
The documents also reveal officials' concerns about the appointment, despite the Government publicly welcoming the move on the grounds it would "add to Lena Wilson's considerable experience".
In an email timed at 8.02am on June 11, Peter Ritchie, an official with the Government's enterprise division in Glasgow requested details of all financial assistance offered to Intertek by SE over a five-year period.
He told colleagues he must have the information at least 30 minutes before the announcement is made.
In another email on June 12, senior Government press officer Neil Trotter asked unnamed colleagues: "Can you share with me what you have said in response to claims of a conflict of interest?"
The message followed criticism of the move by Scottish LibDem leader Willie Rennie, who warned of a possible conflict of interest, and Labour MSP John Park, who said it was "not sensible" for Ms Wilson to take up the new role.
In all, six named officials, plus others whose names have been withheld, were involved in preparing "lines to take" on the appointment.
Last night the Scottish Government refused to comment and Scottish Enterprise was unavailable.
Ms Wilson stepped down from the board of The Prince's Scottish Youth Business Trust, a charity that provides finance and professional support to 18 to 25-year-olds to run their own business, to take up the Intertek role.
It was the first time a SE serving chief executive had taken a directorship of a publicly quoted company.
Labour MSP Rhoda Grant said: "This appointment clearly worried officials and the fact that John Swinney was involved shows just how controversial this appointment was.
"Since her appointment, Scotland has entered a double-dip recession, youth unemployment remains at a record high and Scottish Enterprise is left with a part-time boss.
"While civil servants championed the prestige for Ms Wilson and Scottish Enterprise, nobody discussed how often she would be away from her desk, or discussing her company's business instead of what she is employed to manage. That says everything we need to know about the priorities for civil servants, the Scottish Government and Scottish Enterprise."
At the time of the appointment the Government stressed Mr Swinney was not involved in the decision but had been informed and was supportive of the move.