The bioactive ethyl acetate phase obtained from the latex of Croton urucurana Baillon afforded a novel orbitide (1), [1-9-NαC]-crourorb A1, that proved active against NCI-ADR/RES (ovary, multidrug-resistance phenotype) cells with the same potency as doxorubicin (positive control) and inactive up to the highest concentration tested against nontumor NIH/3T3 cells. The structure elucidation was based on 1D and 2D NMR spectroscopy, further supported by HRESIMS data and by application of Marfey's method for determination of the absolute configuration of its amino acid residues. This is the first orbitide obtained from C. urucurana.