The first measurement of exclusive photoproduction of ρ 0 mesons associated with leading neutrons at HERA is presented. The data are taken with the H1 detector in the years 2006-2007 at √ s = 319 GeV and correspond to an integrated luminosity of 1.16 pb −1 . ρ 0 mesons are reconstructed from their decays to pions in the central tracking chamber, while leading neutrons carrying a large fraction of the incoming proton momentum, x L > 0.35, are detected in the Forward Neutron Calorimeter. The phase space of the measurement is defined by the photon virtuality Q 2 < 2 GeV 2 , the total energy of the photon-proton system 20 < W γp < 100 GeV and the polar angle of the leading neutron, θ n < 0.75 mrad. The cross section of the reaction γ p → ρ 0 nY , where Y is a small mass system escaping undetected in the proton direction, is measured as a function of the neutron energy, of the effective mass of the π + π − system as well as of the transverse momentum squared, p 2 t , and of the pseudorapidity η of ρ meson. The data are interpreted in terms of the double peripheral process, involving pion exchange at the proton vertex followed by elastic photoproduction of a ρ meson on the virtual pion. In the framework of OPE approach elastic cross section of photon-pion scattering, σ el (γπ + → ρ 0 π + ) at average energy W γπ = 22 GeV is extracted.