Commercial NMC cells of 18650-type based on a Lix(Ni0.5Mn0.3Co0.2)O2 cathode and a graphitic anode were studied in situ using a combination of high-resolution monochromatic neutron powder diffraction and electrochemical analysis. The structural changes of the electrode materials during cell charge/discharge have been determined using Rietveld refinement and single profile decomposition techniques. A transformation of the graphitic anode to LiC12 and LiC6 through the formation of higher ordered lithium intercalated carbons was observed. A different behavior of electrochemically-driven lattice distortion was observed for NMC material in comparison to LixCoO2 and its influence on the overall cell performance has been discussed in brief. Detailed analysis of the structural changes in the Lix(Ni0.5Mn0.3Co0.2)O2 cathode material revealed reversible Li/Ni cation mixing (5.6(8)%), which is state-of-charge independent below 1600 mAh and vanishing above 1800 mAh (∼0.8Qmax).