Graph is an atomic expression. It is not a Mathematica expression made up of a head and multiple "arguments", even though sometimes it vaguely looks like one. Instead you should treat it as an indivisible unit.
Use VertexList, EdgeList, PropertyValue, etc. to extract information from it.
We should distinguish between a truly atomic Graph object, and a compound expression with head Graph. When you type Graph[{1,2,3},{1<->2}] in Mathematica, you are indeed writing a compound expression which can be manipulated like any other. For example:
g = Hold@Graph[{1, 2, 3}, {1 <-> 2}]
(* Hold[Graph[{1, 2, 3}, {1 <-> 2}]] *)
g[[1, 1]]
(* {1, 2, 3} *)
However, this compound expression immediately evaluates to an atomic Graph:
AtomQ@ReleaseHold[g]
(* True *)
After that it is no longer possible to access its parts (because it has no parts).
As you can see, not every expression with Head Graph is an atomic Graph object. To test if one is, use the GraphQ function. For example:
GraphQ@Graph[{1, 2, 3}, {2 <-> 3}]
(* True *)
GraphQ@Graph[asd]
(* False *)
Graph[asd] is not a valid way to construct a graph, so instead of evaluating to a true graph, it stays as a compound expression.
To make this answer complete, I should note that atomic Graph objects do in fact have a representation as a compound expression, but these are not meant to be used by end users. They are used internally for serialization, such as storing a graph in a notebook, sending it through MathLink, Compressing it, etc. See my two answers here on how to get to it.
Since these representations are not meant for end users, they are undocumented (meaning that you might easily encounter unexpected forms – don't assume that inspecting one graph tells you how others are represented) and may be different between different Mathematica versions.
Graph[]is an atomic object (see this related thread), you cannot use things likeApply[]orPart[]on it. Instead, useVertexList[]andEdgeList[]to extract vertices and edges, respectively. Additionally, look upPropertyValue[]. Someone else might want to write an elaboration of this comment. – J. M.'s missing motivation Feb 24 '16 at 14:133) When you see good questions and answers, vote them up by clicking the gray triangles, because the credibility of the system is based on the reputation gained by users sharing their knowledge. Also, please remember to accept the answer, if any, that solves your problem, by clicking the checkmark sign! – Feb 24 '16 at 14:47