This paper describes a novel promising film based on the flowerlike CuWO4 structure, and applied to photoelectrochemical (PEC) water splitting as a photoanode first. The growth mechanism and microstructure of CuWO4 are discussed in detail. The PEC measurements indicate that flowerlike CuWO(4 )exhibited a photocurrent density of 0.58 mA/cm(2) at 0.8 V versus RHE. When coupled with CdS and FeOOH layers, the triple CuWO4/CdS/FeOOH photoanode exhibited further improved PEC performance with a higher photocurrent density of about 2.05 mA/cm(2 )at 0.8 V versus RHE and excellent operation stability. The remarkable PEC performance stems from several crucial factors: (i) ideal band gap; (ii) improved light absorption; (iii) efficient charge-hole pair separation and collection.