The global increase in lignocellulosic ethanol production goes in tandem with an increase in lignin-rich stillage that remains underutilized to date. Anaerobic digestion could valorize residual (biodegradable) organic fractions into biogas, leaving a lignin-rich digested stillage (LRDS). This LRDS from the lignocellulosic ethanol production has been assessed as a feedstock for slow and fast pyrolysis in earlier studies, with the intention to increase the overall output of useful products or energy carriers from the starting material. While using this lignin-rich feedstock, ex situ catalytic vapor-phase upgrading (VPU) of fast pyrolysis vapors with fractional condensation was conducted over Na/ZSM-5, H/ZSM-5, and Fe/ZSM-5 catalysts. Semicontinuous fast pyrolysis experiments have been carried out at a reaction temperature of 480 degrees C in a mechanically stirred sand bed, which was connected directly to a fixed bed of catalyst particles for ex situ upgrading of the fast pyrolysis vapors. The carbon and mass yields in heavy phase liquids decreased after catalytic VPU (mass: ca. 8-11 wt %; carbon: ca. 11-15 wt %), compared to noncatalytic pyrolysis (mass: ca. 18 wt %; carbon: ca. 23 wt %). However, the yield in specific compounds, that is, alkylphenols and aromatics such as BTX, increased much upon catalytic VPU (especially for Fe/ZSM-5). For Fe/ZSM-5, the concentration in alkylphenols and aromatics was 20.8 wt % on liquid basis and the yield was 1.7 wt % on as-received (a.r.) feedstock basis. For noncatalytic pyrolysis, the concentration in alkylphenols and aromatics was 2.1 wt % (liquid basis) with a yield of 0.4 wt % (a.r. feedstock basis). This study thus demonstrates the potential of (modified) catalysts to upgrade lignin pyrolysis vapors.