In 1916 Olave was enrolled as a Guide. Love and service to God, country and other people were the powers that directed her life.

In 1938 the World Chief Guide went with BP, whose health was failing, to their home 'Paxtu' in Kenya. There they lived the open-air life they both loved, and there two years later Robert Baden-Powell died.

In 1973 the United Nations honoured Olave Baden Powell as Woman of the Year by awarding her the Ceres Medal.

She was decorated with national honours by Chile, Finland, Greece, Haiti, Japan, Lebanon, Panama, Peru, Poland and the United Kingdom.

She was an indefatigable traveller, visiting 111 countries in all.

Her role in Guiding changed with age, but she constantly kept its growth foremost in her life, identifying opportunities for established Guiding countries to assist new ones. She redirected many personal gifts to Guiding. She told would-be flower donors that "flowers do not go with Guide uniform", and "souvenirs are an embarrassment to carry around when one is travelling light, hurrying from city to city by car or train or plane for weeks and months on end ". Australian Guiding developed a unique gift idea, 'Ice-cream for the Chief', and American Scouts generously supplied a credit card for her use from 1968 until her death.