Aluminum based reactive nanomaterials have extensive applications in many fields including solid propellants, pyrotechnics, and catalytic reactions. One recent example is the novel concept of using nanostructured energetic particles for energy storage where the controlled exothermic reaction is the key to control the energy release process. It is of primary interest to understand the thermodynamics, kinetics, morphological and structural properties of these particles during the exothermic reaction. While the physiochemical properties of the monometallic powders are determined only by their size, the properties of bimetallic nanoalloys can be also engineered by their constituent compositions. This thesis conducts a systematic experimental investigation of the oxidation, ignition, and combustion of nano aluminum particles (nAl) and nanoalloys such as nanoscale aluminium-copper (n-AlCu) and aluminium-zinc (n-AlZn). The oxidation experiments are conducted by a TGA/DSC system with detailed characterisation of particles before and after the experiments by scanning electron microscopy (SEM), transmission electron microscopy (TEM), the Nanosizer, Brunauer–Emmett–Teller (BET), energy dispersive X-ray spectroscopy (EDS) and powder X-ray diffractionmetry (XRD). In the TGA/DSC analysis, nanomaterials are oxidized either at constant temperature or under different heating rates in the controlled atmosphere of air or nitrogen. A unique early ignition reaction is observed at the high heating rates for nAl and n-AlCu, which is associated with the effect of polymorphic phase transformation of the alumina shell and the early melting of the aluminum core. Different to the conventional shrink-core concept, hollow structures, i.e. nanoholes, in the central regions of nAl are observed and a phenomenal model is proposed. The comparison of the thermal-chemical characteristics of different nanomaterials reveals some unique 5 features related to nano-alloys such as increased reactivity. A preliminary combustion experiment on feeding nanoparticles in a methane stream is performed with a Bunsen burner setup, where the burning characteristics of different nanoparticles are analysed.