We present a high-accuracy calculation of the deuteron structure radius in chiral effective field theory. Our analysis employs the state-of-the-art semilocal two-nucleon potentials and takes into account two-body contributions to the charge density operators up to fifth order in the chiral expansion. The strength of the fifth-order short-range two-body contribution to the charge density operator is adjusted to the experimental data on the deuteron charge form factor. A detailed error analysis is performed by propagating the statistical uncertainties of the low-energy constants entering the two-nucleon potentials and by estimating errors from the truncation of the chiral expansion as well as from uncertainties in the nucleon form factors. Using the predicted value for the deuteron structure radius together with the very accurate atomic data for the difference of the deuteron and proton charge radii we, for the first time, extract the charge radius of the neutron from light nuclei. The extracted value reads $r_n^2 = - 0.106 substack{ +0.007 -0.005} , text{fm}^2$ and its magnitude is about $1.7sigma$ smaller than the current value given by the Particle Data Group. In addition, given the high accuracy of the calculated deuteron charge form factor and its careful and systematic error analysis, our results open the way for an accurate determination of the nucleon form factors from elastic electron-deuteron scattering data measured at the Mainz Microtron and other experimental facilities.