Woolen bun shaped CdS microspheres (2-5 mu m) wrapped by highly crystalline one dimensional CdS nanowires (length = 8-10 mu m and diameter similar to 80 nm) are synthesized via anodic alumina membrane to achieve the best photoactivity for the decomposition of rhodamine B (50 mu M) and methylene blue (20 mu M) dyes using sunlight (50 mWcm(-2)) irradiations. The higher number of surface exposed molecules for improved interactions with dye molecules in CdS nanowires led to its excellent photocatalytic performance over its spherical [cubic (similar to 12 nm) and hexagonal (similar to 15 nm) phase] and rod like (170 nm x 10 nm) morphology. Though of having less surface area (35.55 < 76 m(2)g(-1)) than nanorods, the crystalline structure with least surface defects, higher spectral response to absorb more light for multiple generation of charge carriers (e(-)-h(+)), and their superior delocalization for better charge separation as evidenced from its maximum (>80%) photoluminescence quenching and higher photoexcited charge carrier relaxation lifetime (3.6 ns) seems to be the cause of its outstanding performance. Many intermediate products and nearly linear increase in CO2 production are quantified during rhodamine B degradation by CdS nanowires under different time periods of sunlight irradiation. (C) 2014 Elsevier B.V. All rights reserved.