The potential energy surfaces of even-even 142-156Ba are investigated in the constrained reflectionasymmetric relativistic mean-field approach with parameter set PK1. It is shown that for the ground states, 142Ba is near spherical,156Ba well quadrupole-deformed, and in between 144-154Ba octupole deformed. In particular, the nuclei 148,150Ba with N=92, 94 have the largest octupole deformations. By including the octupole degree of freedom, energy gaps N = 88, N = 94 and Z = 56 near Fermi surfaces for the singleparticle levels in 148Ba with β2 ~ 0.26 and β3 ~ 0.17 are found. Furthermore, the performance of the octupole deformation driving pairs (ν2f7/2, ν1i13/2) and (π2d5/2, π1h11/2) is demonstrated by analyzing the singleparticle levels near Fermi surfaces in 148Ba.