The Pt layer deposited on a cylindrical micro cavity patterned Petri dish, which is produced using a one-step solvent-immersion phase separation, is fabricated for the first time as an FTO-free counter electrode (CE) for dye-sensitized solar cells (DSCs). Due to the high specific active surface area of the Pt-deposited honeycomb substrate CE, the efficiency of the DSC using the developed CE substrate is enhanced by 14.5% compared with the device using a Pt-sputtered flat substrate. This design strategy has potential in fabricating highly efficient and low-cost CE materials with FTO-free substrates for DSCs.