The gas phase reactivity of C₂H₂N⁺ with C₂H₄ is studied using a combined experimental and theoretical approach through guided ion beam mass spectrometry (GIB-MS) and ab initio calculations. Results indicate the formation of C₃H₅⁺, C₂H₄⁺, C₄H₅N⁺ and C₃H₃⁺ as major products, in addition to minor generation of C₂H₃⁺, C₂H₄N⁺, C₄H₄N⁺, C₃H₂N⁺, and CH₃⁺. Theoretical calculations show that reaction proceeds via formation and subsequent rearrangements of a [C₄H₆N]⁺ adduct. In the quest to probe its singlet electronic state hypersurface, the most relevant stationary points along the reaction pathway leading to the various products are located and optimized. The results of our calculations at the MP2/6-311++G(d,p) level were found to be in agreement with our experimental findings, as well as with the derived enthalpies of reaction for the designated reaction channels. The present study provides substantial new insights on the formation of complex organics in Titan’s ionosphere detected by the Ion and Neutral Mass Spectrometer (INMS) onboard the Cassini spacecraft. These pathways might also be of relevance for the generation of long chain carbon-nitrogen bearing compounds in low-temperature environments e.g. the interstellar medium or circumstellar envelopes.