The Al-doped BiFeO
3
, i.e., BFA
x
O powder samples with
x
= 0, 0.025, 0.05, and 0.1, were prepared via the hydrothermal route. The effects of Al substitution on the structural, electrical, and optical properties of BFA
x
O samples were investigated. It is found that the substitution of Al ions at B-site of BiFeO
3
did not cause structural change and it still retains the rhombohedral perovskite structure with
R3c
symmetry, which was confirmed by the X-ray diffraction (XRD) and Raman measurements. X-ray absorption fine structure (XAFS) above the Fe
K
-edge and Bi
L
3
-edge in BFA
x
O powders was also measured and analyzed. Fe ions exhibit mixed valence states (Fe
2+
/Fe
3+
) while Bi ions keep the + 3 valence state in all the samples. Fe
K
-edge XAFS also indicated that there was a competition between hybridization of Fe 3
d
and Al 3
d
with O 2
p
orbitals and occurrence of the more 4
p
orbitals with Al doping. The Bi
L
3
-edge XAFS revealed that transition from 2
p
3/2
to 6
d
state increased, so did the energy of 6
d
state. Besides, Al ion doping affected both the nearest-neighbor and next-nearest coordination shells of Fe atom and nearest-neighbor shells of Bi atom. Ultraviolet-visible (UV-Vis) spectroscopy results show the BFA
x
O prepared by hydrothermal method could be an appropriate visible-light photocatalytic material.