We present a stacking technique for making the stacked opaline films using the colloid multilayers as building blocks. The process of stacking was easily confirmed by monitoring the intensities and positions of Bragg diffraction peaks due to the ordered structures of the multilayers. The stacking of the same kind of multilayers led to the increased intensities of the peaks corresponding to the repeated cycles of stacking, while the stacking of the different kind of multilayers led to the overlapping of each diffraction peak. In the electrochemical deposition of nickel into the interstitial spaces of the opaline films thus obtained, we found the interesting current-time responses with the oscillatory behavior. The simple geometrical considerations of the ordered opaline structure could well explain that the periodic current oscillation was caused by the periodic changes of the electrodeposited area of the interstices. These electrochemical signals would be useful for the control of the positions and chemical compositions of deposited materials every layers and/or multilayers as building blocks.