We report the first observation of the charge symmetry breaking d + d → 4 He + π 0 reaction near threshold at the Indiana University Cyclotron Facility. Kinematic reconstruction permitted the separation of 4 He + π 0 events from double radiative capture 4 He + γ + γ events. We measured total cross sections for neutral pion production of 12.7 ± 2.2 pb at 228.5 MeV and 15.1 ± 3.1 pb at 231.8 MeV. The uncertainty is dominated by statistical errors.Charge symmetry is the approximate symmetry of the strong interaction under a specific isospin rotation that interchanges down and up quarks [1,2]. This symmetry is broken by the different masses of the down and up quarks (m d > m u ) and by their electromagnetic interactions. The combination of these two mechanisms leads, for example, to the neutron being heavier than the proton. Within the framework of chiral effective field theory [3,4], additional experimental information on the relative contributions of these two mechanisms to charge symmetry breaking (CSB) must, in leading order, come from pion-nucleon scattering. Direct experimental evidence is restricted to elastic scattering and charge exchange experiments with low-energy charged pions where the interpretation is complicated by corrections for the neutron-proton mass difference and electromagnetic interactions between the pions and nucleons [5,6]. Reactions in which a π 0 is emitted after being created by one nucleon and rescattered by a second are particularly clean. One 1