The development of zeolites possessing dendritic features represents a great opportunity for the design of novel materials with applications in a large variety of fields and, in particular, in the energy sector to afford its transition towards a low carbon system. In the current work, ZSM-5 zeolite showing a dendritic 3D nanoarchitecture has been synthesized by the functionalization of protozeolitic nanounits with an amphiphilic organosilane, which provokes the branched aggregative growth of zeolite embryos. Dendritic ZSM-5 exhibits outstanding accessibility arising from a highly interconnected network of radially-oriented mesopores (3 – 10 nm) and large cavities (20 – 80 nm), which add to the zeolitic micropores, thus showing a well-defined trimodal pore size distribution. These singular features provide dendritic ZSM-5 with sharply enhanced performance in comparison with nano- and hierarchical reference materials when tested in a number of energy related applications, such as VOCs (toluene) adsorption (improved capacity), plastics (low-density polyethylene) catalytic cracking (boosted activity) and hydrogen production by methane catalytic decomposition (higher activity and deactivation resistance).