Who was the British PM at the time right before Sierra Leone got it's independence?

The British Prime Minister at the time right before Sierra Leone gained independence in 1961 was Harold Macmillan.

Was he also looking after Ghana before they got their independence?

Yes, Harold Macmillan was serving as the British Prime Minister during the periods leading up to the independence of both Ghana and Sierra Leone. Ghana became independent in 1957, during Macmillan's tenure, and Sierra Leone gained independence in 1961. Macmillan was involved in overseeing the decolonization process in both countries.