Photoelectrochemical (PEC) water splitting is widely regarded as an effective process for sustainable storage of solar energy as chemical energy in the form of H2. The efficiency of this process depends upon the light absorption, charge injection, and charge separation efficiency of the photoanode material used. In this work, doping hematite with 1% tin and loading with NiFe-layered double hydroxide (LDH) co-catalyst has been done to improve the charge transport properties. To enhance the PEC performance and study the effect of precursor concentration, NiFe-LDH at two different concentrations (low and high) was coated on Sn-doped hematite. A high photocurrent density ca. 2.9 mA/cm2 at 1.8 V vs reversible hydrogen electrode (RHE) and a 170 mV cathodic shift in onset potential compared to pristine hematite (0.22 mA/cm2 at 1.8 V vs RHE) was recorded for Sn-doped hematite coated with low precursor concentration. The enhanced PEC activity can be attributed to the synergistic effect of Sn doping and NiFe-LDH co-catalyst on hematite, which contributes to an efficient separation of the photogenerated charge carriers and reduces hole accumulation at the surface. However, for the high precursor concentration case, the formation of a thick film of NiFe-LDH results in a comparatively lower current density (0.85 mA/cm2 at 1.8 V vs RHE). The results obtained show that NiFe-LDH can be used as an effective co-catalyst to significantly enhance the charge transport properties of tin-doped hematite. A charge transfer mechanism of the developed photoanodes is also discussed in detail.