We present a comprehensive experimental and ab initio study of the S=1/2Mo5+ system, KMoOP2O7, and show that it realizes the S=12 Heisenberg chain antiferromagnet model. Powder neutron diffraction reveals that KMoOP2O7 forms a magnetic network comprised of pairs of Mo5+ chains within its monoclinic P21/n structure. Antiferromagnetic interactions within the Mo5+ chains are identified through magnetometry measurements and confirmed by analysis of the magnetic specific heat. The latter reveals a broad feature centered on TN=0.54 K, which we ascribe to the onset of long-range antiferromagnetic order. No magnetic Bragg scattering is observed in powder neutron-diffraction data collected at 0.05 K, however, which is consistent with a strongly suppressed ordered moment with an upper limit μord<0.15μB. The one-dimensional character of the magnetic correlations in KMoOP2O7 is verified through analysis of inelastic neutron-scattering data, resulting in a model with J2≈34 K and J1≈-2 K for the intrachain and interchain exchange interactions, respectively. The origin of these experimental findings are addressed through density-functional theory calculations