We describe a novel technique for probing the statistical properties of cosmic magnetic fields based on radio polarimetry data. Second‐order magnetic field statistics like the power spectrum cannot always distinguish between magnetic fields with essentially different spatial structure. Synchrotron polarimetry naturally allows certain fourth‐order magnetic field statistics to be inferred from observational data, which lifts this degeneracy and can thereby help us gain a better picture of the structure of the cosmic fields and test theoretical scenarios describing magnetic turbulence. In this work we show that a fourth‐order correlator of specific physical interest, the tension force spectrum, can be recovered from the polarized synchrotron emission data. We develop an estimator for this quantity based on polarized emission observations in the Faraday rotation free frequency regime. We consider two cases: a statistically isotropic field distribution, and a statistically isotropic field superimposed on a weak mean field. In both cases the tension force power spectrum is measurable; in the latter case, the magnetic power spectrum may also be obtainable. The method is exact in the idealized case of a homogeneous relativistic electron distribution that has a power‐law energy spectrum with a spectral index of p= 3, and assumes statistical isotropy of the turbulent field. We carry out numerical tests of our method using synthetic polarized emission data generated from numerically simulated magnetic fields. We show that the method is valid, that it is not prohibitively sensitive to the value of the electron spectral index p, and that the observed tension force spectrum allows one to distinguish between e.g. a randomly tangled magnetic field (a default assumption in many studies) and a field organized in folded flux sheets or filaments.