Dinucleoside 5’,5’‐polyphosphates (Np n Ns) play essential roles in various biological processes. Access to these high value‐added compounds, while avoiding the many drawbacks of solution phase synthesis, is a challenge that has been overcome thanks to mechanochemistry. A straightforward solid‐state synthesis based on activation of phosphate or pyrophosphate sodium salts to their diimidazolides, followed by coupling with commercially available nucleotides, under air conditions, gave symmetrical Np n Ns. The scope ranged from Np 3 Ns to highly challenging Np 6 Ns. The methodology has also been implemented using medronic acid and imidodiphosphate to obtain Np n Ns analogues, some of which are unprecedented.