Although PubMed is essentially a way of accessing the MEDLINE database, it actually contains some additional content, including references to some books and chapters, in-process and 'ahead of print' citations, and some articles which lie slightly outside of the subject scope of MEDLINE, such as those on astrophysics.
Note, however, that UCL's access to MEDLINE via Ovid includes in-process and 'ahead of print' citations so it is unlikely that you would have a need to search both PubMed and Ovid MEDLINE.
Tip: PubMed is a great interface for carrying out a basic scoping search, or if you wish to identify a limited number of key references. MEDLINE via Ovid is recommended if you wish to carry out a comprehensive, structured or systematic search.