End-to-end dimers of gold nanorods are predicted to be excellent substrates for surface-enhanced spectroscopy. However, the synthesis of solution-stable end-to-end dimers remains challenging. We exploit the pH-dependent configurational change of polyelectrolytes to initiate and terminate the gold nanorod assembly formation to produce end-to-end linked dimers in high yield. The gold nanorods are first overcoated with a polyelectrolyte, and the end-to-end attachment is initiated by adding a thiol linker in acidic medium. The assembly formation is then terminated at the dimer stage by changing the pH of the medium by the addition of an appropriate amount of 1,4-diazabicyclo[2.2.2]octane (DABCO).The nanorod dimers synthesized here are stable in solution for a week without any additional surface encapsulation.