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In the area under tree rows of alley cropping systems, coarse plant material as well as pruning material or stones may be present, so the use of a mower equipped with chains as cutting a tool could be advantageous. A mower designed for under-row weed control in orchards, equipped with an automatic tree-skipping mechanism, was modified by replacing blades with chains with the aim of evaluating its performance in an alley cropping system. A first trial was carried out in an open field to preliminarily compare the chain mower with the version equipped with blades in relation to different settings of working speed (1.6 and 2.4 km·h−1) and rotation speed of the cutting tool (1830 and 2500 rpm). Weed biomass reduction, weed cover reduction, weed height reduction, weed biomass regrowth, and clipping size were assessed. In a second trial, the performance of the mowers with different setting configurations was assessed in an alley cropping system under a more critical environmental condition for mowing, i.e., the presence of dew. Weed biomass reduction, weed cover reduction, weed height reduction, and the mowers’ field capacity with different working speed settings were assessed. No major differences emerged between the mowers and the chain mower performance was comparable to that of the standard blade mower. The setting with the high working speed and high rotation speed of the cutting tool turns out to be the best compromise, obtaining a weed biomass reduction of 59.6%, a weed cover reduction of 40.9%, and a higher field capacity compared to the setting with the low working speed, with an increase of 47.9%.