Functional complex-oxide materials show a wide variety of properties and behaviors that cannot be found in any other class of materials, including high-temperature superconductivity and colossal magneto resistance. Consequently, this group of oxide materials has become the focus of many experimental as well as theoretical studies, aiming at understanding the fundamental mechanisms and properties that govern these complex structures. Here, we will review our high-resolution Z-contrast imaging and electron energy-loss studies of two complex-oxide materials systems, more specifically low-angle tilt grain-boundaries in YBa(2)Cu(3)O(7) (YBCO), and the spin-state transition in LaCoO(3). It will be shown that the O K-edge pre-peak can be used to quantify the hole-concentration in the vicinity of the dislocation core in YBCO, as well as to determine the Co(3+) spin-state in LaCoO(3).