2D nanodendrites (NDs) and nanosheets (NSs) have been regarded as efficient nanocatalysts for enhancing the electrocatalytic performance due to their low coordinated sites and abundant electrocatalytic centers. Nevertheless, it remains challenging to construct advanced NDs and NSs in a single reaction system. Herein, by tuning the volume ratios of mixed solvents, the reduction and diffusion rate of Sn2+ on Pd NSs template was rationally controlled to prepare PdSn NDs and PdSn NSs. Ascribed to the open 2D nanostructure, high specific surface area, and robust synergistic effect, the as-prepared PdSn NDs and PdSn NSs exhibited distinguished electrocatalytic activities for ethylene glycol oxidation reaction (EGOR) and ethanol oxidation reaction (EOR), as well as commendable electrocatalytic durability, which were far superior to the Pd NSs and commercial Pd/C. In addition, the PdSn NDs exhibited enhanced reaction kinetics because the characteristic branch structure exposed a high density of active sites. This work may provide significant guidance for preparing excellent nanocatalysts with various morphological features by simply optimizing the content of the coexisting solvents.