In this work, we investigate the B s → V S decays in the perturbative QCD approach, where V and S denote the vector meson and scalar meson respectively. Based on the two-quark structure, considering two different scenarios for describing the scalar mesons, we calculate the branching fractions and the direct CP asymmetries of all B s → V S decays. Most branching fractions are predicted to be at 10 −7 to 10 −5 , which could be measured in the LHCb and Belle-II experiments, especially for these color-allowed B s → κ(800)(K * 0 (1430))K * decays. It is found that the branching fractions of B s → K * 0 0 (1430) K * 0 and B s → K * + 0 (1430) K * − are very sensitive to the scenarios, which can be used to determine whether K * 0 0 (1430) belongs to the ground state or the first excited state, if the data were available. We also note that some decays have large direct CP asymmetries, some of which are also sensitive to the scenarios, such as the B s → a + 0 (1450)K * − and the B s → f 0 (1500)K * 0 decays. Since the experimental measurements of B s → V S decays are on the way, combined with the available data in the future, we expect the theoretical predictions will shed light on the structure of the scalar mesons.