Finite groups always have a chief series, though infinite groups need not have a chief series. For example, the group of integers Z with addition as the operation does not have a chief series. To see this, note Z is cyclic and abelian, and so all of its subgroups are normal and cyclic as well. Supposing there exists a chief series Ni leads to an immediate contradiction: N1 is cyclic and thus is generated by some integer a, however the subgroup generated by 2a is a nontrivial normal subgroup properly contained in N1, contradicting the definition of a chief series.
When a chief series for a group exists, it is generally not unique. However, a form of the Jordan–Hölder theorem states that the chief factors of a group are unique up to isomorphism, independent of the particular chief series they are constructed from[1] In particular, the number of chief factors is an invariant of the group G, as well as the isomorphism classes of the chief factors and their multiplicities.
In abelian groups, chief series and composition series are identical, as all subgroups are normal.
Given any normal subgroup N ⊆ G, one can always find a chief series in which N is one of the elements (assuming a chief series for G exists in the first place.) Also, if G has a chief series and N is normal in G, then both N and G/N have chief series. The converse also holds: if N is normal in G and both N and G/N have chief series, G has a chief series as well.