This tutorial review compiles recent experimental and theoretical studies on the formation of polyacetylenes (H(CC)_nH) and cyanopolyacetylenes (H(CC)_nCN) together with their methyl-substituted counterparts (CH₃(CC)_nH, CH₃(CC)_nCN) as probed under single collision conditions in crossed beam studies via the elementary reactions of ethynyl (CCH) and cyano radicals (CN) with unsaturated hydrocarbons. The role of these key reaction classes in the chemical evolution of Titan's orange-brownish haze layers is also discussed. We further comment on astrobiological implications of our findings with respect to proto-Earth and present a brief outlook on future research directions.