The search for new sources of high-quality non-crystalline silica as a construction material for high-performance concrete has attracted the interest of researchers for several decades. Numerous investigations have shown that highly reactive silica can be produced from rice husk, an agricultural waste that is abundantly available in the world. Among others, the production of rice husk ash (RHA) by chemical washing with hydrochloric acid prior to the controlled combustion process has been reported to provide higher reactivity because such a process removes alkali metal impurities from RHA and provides an amorphous structure with higher surface area. This paper presents an experimental work in which a highly reactive rice husk ash (TRHA) is prepared and evaluated as a replacement for Portland cement in high-performance concretes. The performance of RHA and TRHA was compared with that of conventional silica fume (SF). Experimental results showed that the increase in compressive strength of concrete with TRHA was clearly observed at all ages, generally higher than 20% of the strength obtained with the control concrete. The increase in flexural strength was even more significant, showing that concrete with RHA, TRHA and SF increased by 20%, 46%, and 36%, respectively. Some synergistic effect was observed when polyethylene–polypropylene fiber was used for concrete with TRHA and SF. The chloride ion penetration results also indicated that the use of TRHA had similar performance compared to that of SF. Based on the results of statistical analysis, the performance of TRHA is found to be identical to that of SF. The use of TRHA should be further promoted considering the economic and environmental impact that will be achieved by utilizing agricultural waste.