Palladium (Pd)-catalyzed reactions mostly show structure sensitivity: i.e., the selectivity and activity of the reactions are highly dependent on the arrangement of Pd atoms. In this regard, branched Pd nanoparticles show enhanced catalytic performance owing to the presence of low coordinated Pd atoms. In this paper, a novel solution-phase synthesis of flower-like Pd nanodendrites using ribonucleic acid (RNA) as a capping agent and ascorbic acid as a reducing agent was described. On the other hand, the co-use of polyvinylpyrrolidone (PVP) and potassium bromide (KBr) instead of RNA at the same synthesis conditions led to cuboid nanoparticles, while the sole use of ascorbic acid resulted in faceted nanoparticles. The formation of nanodendritic morphology was attributed to the RNA-assisted growth through particle attachment. This scenario was supported by TEM analysis that demonstrated the aggregation of small particles to form larger nanoparticles at the onset of the reaction. The shape and size of the nanoparticles could be readily tuned by the RNA content used. XPS confirmed the formation of metallic Pd nanoparticles. The presence of crystalline planes of {1 1 1), (2 0 0), (2 2 0), (3 1 1) and (2 2 2) was demonstrated by XRD and SAED analyses. The Pd nanodendrites were used for the reduction of p-nitrophenol (PNP) and 2,4,6-trinitrotoluene (TNT), and reduction rate constants (k) were calculated as 1.078 min(-1) (normalized rate constant, k(nor) = 59.66 mmol(-1) s(-1)) for PNP and 0.3181 min(-1) (k(nor) = 17.6 mmol(-1) s(-1)) for TNT with the corresponding turnover frequencies (TOFs) as 16.06 and 40.80 h(-1), respectively. (C) 2019 Elsevier Inc. All rights reserved.