Yolk/shell particles composed of a submicrometer-sized movable core and a silica shell are promising building blocks for novel optical colloidal crystals, because the locations of cores in the shell compartment can be reversibly changed by using external stimuli. Two dimensional arrays of yolk/shell particles incorporating movable cores were prepared by a self-assembly method. The movable cores of colloidal crystals in water could be observed with an optical microscope under application of external electric field. The motions of inner silica cores depended on the electric field strength and frequency and were categorized into three cases: (1) Random Brownian motion, (2) anisotropic motion of cores moving in a direction orthogonal to a field, and (3) suppressed motion fixed in the center of shell compartment. Random Brownian motion of cores was scarcely affected by field strength when a high frequency (in the MHz range) electric field was applied. On the other hand, an increase in field strength at low-frequency fields (kHz) transiently changed the core motion from (1) to (2) and a further increase in field strength changed it from (2) to (3). When the silica core was incorporated in a large void a stronger electric field was needed to suppress its motion than when it was in a small void. The high responsivity to electric fields in a low-frequency range indicated the importance of electric double layer (EDL) interaction between core and inner shell in controlling the core location in yolk/shell colloidal crystals. It was also shown that movable titania cores in yolk/shell particles required a low-frequency field with a high strength to change from the random to anisotropic motion. The result suggested that the electrostatic interaction between EDLs of the silica core and the inner silica wall could be stronger than that between EDLs of the titania core and the silica shell.