A series of pyramid-surface TiO2/Ti electrodes were proposed, fabricated, and used in a rotating disk photoelectrocatalytic (PEC) reactor to treat rhodamine B (RB) solution. Compared with conventional planar electrode, pyramid-surface electrode exhibited much lower light reflectivity, larger photocurrent, and better treatment efficiency. For samples containing 20 to 150 mg L-1 RB, 100 98% color removal, and 8-730% COD removal were obtained in 150 min using 1/3 (h/w) pyramid-surface electrode, much higher than 98-77% and 48-9% obtained by a conventional planer electrode. The excellent treatment performance attributed to two major reasons: (a) enhanced light harvest resulted from multiple reflections of irradiation light on the pyramid-surface, and (b) enlarged electrode surface area enabling the electrode to carry more TiO2 catalyst and pollutants for treatment. Experimental results also showed that the pyramid-surface electrode consumed less power and exhibited superior performance when treating high concentration wastewater. (C) 2011 American Institute of Chemical Engineers AIChE J, 58: 24482455, 2012