We report on an experimental study of quantum transport of atoms in variable periodic optical potentials. The band structure of both ratchet-type asymmetric and symmetric lattice potentials is explored. The variable atom potential is realized by superimposing a conventional standing wave potential of lambda/2 spatial periodicity with a fourth-order multiphoton potential of lambda/4 periodicity. We find that the Landau-Zener tunneling rate between the first and the second excited Bloch band depends critically on the relative phase between the two spatial lattice harmonics.