In the present work, a dual-modified waxy rice starch (OOWRS) fabricated with OSA and ozone was successfully used to stabilize the O/W Pickering emulsion. The molecular structure, surface properties, and underlying stabilizing mechanism were systematically investigated. The results showed that oxidation occurring on the surface of OSA-modified waxy rice starch (OSAWRS) resulted in the presence of indentations and cracks. The relative crystallinity of starch was generally decreased with increasing degree of oxidation. Due to the introduction of carbonyl and the variation in surface structure, the hydrophobicity and acidity of OSAWRS were significantly enhanced after the ozone treatment. Remarkably, OOWRS stabilized Pickering emulsion exhibited a feature of typical O/W emulsion, and the 0.5 h and 1 h OOWRS emulsion exhibited a more uniform droplet size as well as a higher surface potential. We also noted that a weak-gel network was formed within the OOWRS emulsion system as the hydrophilic starch chains played a bridging role. Two reasons for the improved stability of the emulsion were the special gel structure and the enhanced electrical repulsion among the droplets. This research provides that ozone-conjugated OSA modification is a promising strategy for improving the emulsion ability of starch-based Pickering emulsions.