The invention provides a photoelectric device including a lithium titanate membrane electrode, which at least comprises a lithium titanate membrane electrode, electrolyte and a counter electrode, wherein a lithium titanate membrane grows on a transparent conductive substrate, and the thickness of the membrane is 1nm-100mum. The lithium titanate membrane comprises a substance with a chemical composition of Li4+xAaTi5-yO12-zBb, wherein A is selected from at least one of H, Na, K, Mg, Ca, Sr, Ba, B, Al, Ga, In, Si, Ge, Sn, Pb, Sc, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, Ru, Rh, Pd, Ag, Cd,La, Ce, Pr, Nd, Sm, Eu, Gd, Er, Tm, Yb, Lu, W, Pt, Au or Bi; B is selected from at least one of N, P, S, Se, F, Cl, Br or I; x, a, y, z and b represent molar percent; and x is larger than or equal to-4 and smaller than or equal to 4, a is larger than or equal to 0 and smaller than or equal to 4, y is larger than or equal to 0 and smaller than or equal to 4, z is larger than or equal to 0 and smaller than or equal to 3 and b is larger than or equal to 0 and smaller than or equal to 4.