Crossed molecular beams experiments were utilized to explore the chemical reaction dynamics of ground-state cyano radicals, CN(X(2)Sigma(+)), with propylene (CH3CHCH2) together with two d3-isotopologues (CD3CHCH2, CH3CDCD2) as potential pathways to form organic nitriles under single collision conditions in the atmosphere of Saturn's moon Titan and in the interstellar medium. On the basis of the center-of-mass translational and angular distributions, the reaction dynamics were deduced to be indirect and commenced via an addition of the electrophilic cyano radical with its radical center to the alpha-carbon atom of the propylene molecule yielding a doublet radical intermediate: CH3CHCH2CN. Crossed beam experiments with propylene-1,1,2-d3 (CH3CDCD2) and propylene-3,3,3-d3 (CD3CHCH2) indicated that the reaction intermediates CH3CDCD2CN (from propylene-1,1,2-d3) and CD3CHCH2CN (from propylene-3,3,3-d3) eject both atomic hydrogen through tight exit transition states located about 40-50 kJ mol(-1) above the separated products: 3-butenenitrile [H2CCDCD2CN] (25%), and cis/trans-2-butenenitrile [CD3CHCHCN] (75%), respectively, plus atomic hydrogen. Applications of our results to the chemical processing of cold molecular clouds like TMC-1 and OMC-1 are also presented.