To understand fully the role of amphibole in the fractionation of Nb/Ta during arc magma evolution, we conducted experiments with mid-K and high-K basalts to determine amphibole/melt Nb, Ta and Ti partition coefficients (DNb, DTa and DTi) at variable conditions of bulk TiO2, P, T, H2O and fO2. The experimental results show that, at crustal pressures, amphibole is the most important crystalline phase in hydrous basaltic systems. The amphibole/melt Nb, Ta, and Ti partitioning results are 0·16–0·90 for DNb, 0·13–0·68 for DTa, 1·81–10·63 for DTi and 0·76–2·81 for DNb/DTa. Bulk TiO2 and fO2 show no observable effects. T and H2O, in addition to the compositions of amphibole and melt, are the main affecting factors. DNb, DTa, DTi and DNb/DTa increase with decreasing temperature, amphibole Mg# and melt H2O content and increasing melt polymerization. During cooling and crystallization of arc magmas at crustal pressures, amphibole Mg# decreases and melt polymerization increases, leading to significant increase in amphibole/melt DNb, DTi and DNb/DTa. Nb/Ta fractionation in evolved melts will thus be enhanced with crystallization progress. Meanwhile, melt H2O content will increase with the degree of crystallization, which slows down the increase in these D values. Therefore, the trend and extent of Nb/Ta fractionation in the melt by amphibole critically depends on temperature and melt H2O content. Only low temperatures or low H2O contents at high temperatures lead to high D values. For arc magmas with an average H2O of ∼3·9 wt %, DNb and DNb/DTa are in general >0·40 and >1·20, respectively, which explains why amphibole fractionation results in lower Nb/Ta ratios in evolved arc magmas. The bulk Nb/Ta fractionation trend during arc magma evolution appears to be generally controlled by fractional crystallization of amphibole. Experimental and modeling results suggest that amphibole is a main fractionating phase during arc magma evolution and continental crust formation.