A new sarpagine-type alkaloid, N-a-methylrauflorine (1), was isolated from Rauvolfia capixabae together with isoreserpiline (2), N-b-oxide-isoreserpiline (3), ajmalicine (4), perakine (5) and vinorine (6) alkaloids. These compounds were characterized based on their spectral data basis, mainly one-(H-1, C-13, APT) and two-dimensional (H-1-H-1-COSY, H-1-H-1-NOESY, HMQC and HMBC) NMR, and mass spectra, also involving comparison with data from the literature.