This study shows the first example of cycloaddition–retro‐electrocyclization (CA‐RE) click reaction involving nitrogen end‐capped push‐pull oligoynes. The reported CA‐RE reaction with TCNE (tetracyanoethylene) is fully regioselective and leads exclusively to the unprecedented TCBD (tetracyanobuta‐1,3‐diene‐2,3‐diyl) end‐capped carbon rods. The molecular structure of the products was unambiguously confirmed using X‐ray single crystal diffraction and their optical and electronic properties were investigated experimentally and rationalized using DFT (density functional theory) calculations.