Nonleptonic weak decays of Ξc into π + and a meson (M )-baryon (B) final state, M B, are analyzed from the viewpoint of probing S = −2 baryon resonances, i.e., Ξ(1620) and Ξ(1690), of which spinparity and other properties are not well known. We argue that the weak decay of Ξc is dominated by a single quark-line diagram, preferred by the Cabibbo-Kobayashi-Maskawa coefficient, color recombination factor, the diquark correlation, and the kinematical condition. The decay process has an advantage of being free from meson resonances in the π + M invariant mass distribution. The invariant mass distribution of the meson-baryon final state is calculated with three different chiral unitary approaches, assuming that the Ξ(1620) and Ξ(1690) resonances have J P = 1/2 − . It is found that a clear peak for the Ξ(1690) is seen in the πΞ andKΛ spectra. We also suggest that the ratios of the πΞ,KΛ andKΣ final states are useful to distinguish whether the peak is originated from the Ξ(1690) resonance or it is aKΣ threshold effect.