In unconventional petroleum reservoirs hydrocarbon fluids are hosted by both mineral and organic matter pores. These pores can have diameters that range from microns to less than a single nanometer and, for unconventional reservoirs, there is evidence that small pores (<20 nm diameter) may constitute a large proportion of the available space. Understanding subsurface volumes and how fluids behave in them can be helpful for predicting hydrocarbon production and storage in the subsurface. One area with knowledge gaps regarding hydrocarbon behavior in small pores is the possibility for mixtures to fractionate (i.e., unmix) based on pore size or pore type. Mixture fractionation as a function of pore size could impact recovery of hydrocarbons, drive compositional shifts during production, and limit fluid storage within candidate reservoirs. To investigate natural gas fractionation in small geologic pores, we applied total neutron scattering to probe methane-ethane mixtures at reservoir pressures (up to ≈30 MPa) and temperature (60°C) within a sample from the Upper Cretaceous Niobrara Formation. Neutron scattering data reveal only minor fractionation occurs between methane and ethane in 20-nm diameter sample mesopores. Increased fractionation is observed for sample micropores, with up to 72% (±1% at 1-sigma) methane found in 2 nm diameter pores following injection of a 50%-50% methane-ethane mixture. These data provide rarely available direct experimental observations of hydrocarbon mixture behavior under nanoconfinement in a sample from an important unconventional petroleum reservoir. Our results are discussed in the context of evaluating hydrocarbon resources in unconventional reservoir meso- and micropores, reconciling observed gas composition changes during production, and more broadly, understanding subsurface pore volumes within an energy storage framework.