If you throw a bunch of carbon, oxygen, and other organic compounds into a vat, you're vastly less likely to get a fully formed human being than, well, a disorganized pile of matter. Usually you wouldn't consider the random clump of molecules more complex -- there are practically an infinite number ways to rearrange a pile into a pile. In contrast, there are many orders of magnitude fewer ways for a human being to emerge.
That said, there is a sense in which the random pile of molecules is more complex. If I want to predict the motion of every (or at least, most) of the molecules in that vat, it's easier to predict the bulk motion of a human than each molecule moving per the Maxwell–Boltzmann distribution.
Similarly, it's easier to compress a static black image than continuous random noise. Notice that a static black image is more organized, more easily compressed, and less likely to occur by random chance (assuming noise is the default). Therefore, a static black image has less entropy. Whether you want to call this state more or less complex is a matter of definition.