Engender, a charity that aims to increase the power and influence of women in society, said it was shocked at the apparent gender imbalance, with women only accounting for 12% of the key posts.
The latest appointments come ahead of the launch of Police Scotland on April 1, in place of the current eight forces.
The figure includes the chief constable Stephen House, four deputy chief constables, six assistant chief constables and the recently announced 14 local commanders.
However, only one of the deputy chief constable posts has been taken up by a woman, Rose Fitzpatrick from the Metropolitan Police.
Kate Thomson, of Dumfries and Galloway Constabulary, and Jeanette McDiarmid, of the Lothian and Borders police force, are new local commanders.
Engender director Niki Kandirikirira said the failure of women to break through in the new force points to a systemic problem within the police.
She said: "Although we don't know what the application process has been like, the lack of women implies that there's something wrong in the way women are progressing within the police.
"There appears to be something systematically wrong and the force should be trying to work out what that is so that it can address it.
"It should be investigating why there are so few women in the top jobs, as should the whole public sector in Scotland."
Scottish Labour MSP Jenny Marra said: "We raised the issue of gender balance within the new structure as part of the legislation, but the SNP believed it wasn't important enough.
"Now we see the reality of this, with only a handful of women at the top of Scotland's police. It is another disappointing missed opportunity for Scotland's women to be fairly represented at the top of one of the most important organisations in Scotland."
Justine Curran, Scotland's only female chief constable within the current forces, has also missed out on a senior role.
It is understood she applied for the role of chief constable and for one of the deputy chief c onstable roles, but failed to secure a spot.
Chief Superintendent David O'Connor, president of the Association of Scottish Police Superintendents (ASPS), said further posts involving chief superintendents and superintendents are expected to be announced shortly – including the appointment of several women.
He said: "ASPS welcomes the recent appointment of local commanders and looks forward to the continuing exercise of allocating chief superintendents and superintendents posts.
"We are aware that a number of these particular posts will be occupied by female officers.
"We believe those appointed have the right balance of skills and experience to lead the service forward and build upon the positive policing results that currently exist."
A spokesman for Police Scotland added: "The local commanders have been appointed on the basis of their experience in policing and skills. They were not appointed on the basis of gender.
"They have existing roles as operational commanders within each of the areas and as such have a continuing relationship with local authorities, fire and health services."
Mr House said: "I am delighted we have this key team now in place. Their work is right at the heart of the new single police service for Scotland and will ensure that we maintain and build on the high quality of policing already in place."