Polyanion phosphate based Li3V2(PO4)3 material has attracted considerable attention as a novel cathode material for potential use in rechargeable lithium ion batteries. The defect chemistry and dopant properties of this material are studied using well-established atomistic scale simulation techniques. The most favourable intrinsic defect process is the Li Frenkel (0.45 eV/defect) ensuring the formation of Li vacancies required for Li diffusion via the vacancy mechanism. Long range lithium paths via the vacancy mechanism were constructed and it is confirmed that the lowest activation energy of migration (0.60 eV) path is three dimensional with curved trajectory. The second most stable defect energy process is calculated to be the anti-site defect, in which Li and V ions exchange their positions (0.91 eV/defect). Tetravalent dopants were considered on both V and P sites in order to form Li vacancies needed for Li diffusion and the Li interstitials to increase the capacity respectively. Doping by Zr on the V site and Si on the P site are calculated to be energetically favourable.