Photoelectrochemical (PEC) water splitting is a promising method for converting solar energy into hydrogen fuel, but how to further improve the efficiency of solar energy conversion is still a large challenge. Here, it is the first time to decorate BiVO4 with Ag and N-doped carbon (BiVO4-C/N-Ag) for efficient solar-to-chemical energy conversion, and we in-depth demonstrated the superiorly of BiVO4-C/N-Ag heterostructure in PEC water splitting system. Polydopamine (PDA) as medium material realized the in-situ anchor of both Ag and N-doped carbon on BiVO4, which significantly boosted the charge injection efficiency (eta(inj)) and charge separation efficiency (eta(sep)) to 88.59% and 29.75% (1.23 V vs. RHE), respectively. The effective function of Ag and N-doped carbon exhibited an obvious influence on the enhancement of PEC performance. The photocurrent density of BiVO4-C/N-Ag increased up to 2.42 mA/cm(2) at 1.23 V vs. RHE, and 7.5-fold IPCE value (30%, 400 nm, 1.23 V vs. RHE) over bare BiVO4 has been achieved, indicating the successful configuration of a promising photoanode in the field of PEC water splitting.