I am reading J. P. Serre's Lie Algebras and Lie Groups and here is how a P. Hall Family is defined:
I failed to understand the motivations of this definition. Could anyone explain it to me? Also, some simple examples of P. Hall Families will also be greatly appreciated.

This is important, for example, for the theory of free Lie algebras, e.g., a P. Hall basis. As with all definitions, the motivation comes afterwards, rarely before. A good reference is the book Free Lie algebras by Christophe Reutenauer. However, also the book J.-P. Serre you are reading gives motivating results afterwards. For an example, see
Examples of Free Lie Algebra