The mechanochemical activation of covalent bonds in bulk polymers is often characterized by low conversions. Here we report that the activation of gem-dibromocyclopropane (gDBC) mechanophores embedded in a poly(1,4-butadiene) (PB) is enhanced when a central gDBC-PB block is flanked by two polystyrene (PS) end blocks in an ABA-type triblock architecture. Electrospinning the PS-(gDBC) PB-PS leads to even greater activation in aligned fiber mats under tension.