A facile and unified approach to the main selaginpulvilin's framework was achieved by catalytic [2 + 2 + 2]-cyclotrimerization of a triyne with monosubtituted alkynes. The reaction proceeded with high "ortho" selectivity by using Wilkinson's catalyst (RhCl(PPh3)3) under ambient conditions with reasonable yields. The scope of the reaction with respect to the alkyne as well as the catalytic system was evaluated. The formal total modular syntheses of selaginpulvilin C and D were accomplished by transformation of the cyclotrimerization's products.