The incorporation of phosphorus and boron into [3]dendralenes provides access to heavy heterodendralenes, a new class of main-group precursor to "doped" polycyclic hydrocarbons. [n]Dendralenes are a core class of unsaturated hydrocarbons built from geminally connected polyenes; the resulting arrangement of conjugated C═C bonds enables [n]dendralenes to undergo reactions that allow rapid access to complex polycyclic compounds. The increasing technological and synthetic importance of main-group-containing polycyclic hydrocarbons and their analogues makes new routes to access such systems highly attractive. Here we report the preparation of the first heavy heterodendralenes in the form of phosphorus- and boron-containing [3]dendralenes, prepared by a ring-opening reaction of a 1,2-phosphaborete. We reveal the electronic effect of P/B incorporation and demonstrate that, like their hydrocarbon analogues, phosphabora[3]dendralenes undergo diene-transmissive cycloaddition chemistry.