The Cabinet Office has issued no specific guidance on CAPTCHAs and it holds no central records of which departmental websites use them. Responsibility for information security and accessibility measures of individual websites lies with the individual Departments.
The overall policy for Government Departments on website registration is set out in the Registration and Authentication e-Government Strategy Framework Policy and Guidelines (Version 3.0, September 2002):
http://www.cabinetoffice.gov.uk/upload/assets/www.cabinetoffice.gov.uk/csia/regandauthentn0209v3.pdf
Government websites should also comply with the Government's website accessibility guidelines:
http://www.cabinetoffice.gov.uk/upload/assets/www.cabinetoffice.gov.uk/publications/government_it/consultations/pdf/delivering_inclusive_websites1.pdf
Copies of both these documents have been placed in the Libraries of the House.