Abundant tuff mineral resources offer a promising solution to the shortage of fly ash (FA) and silica fume (SF) resources as emerging supplementary cementitious materials. However, a lack of clarity on its hydration mechanism has hindered its practical engineering application. In this study, high SiO2-content tuff powder (TP) was examined to assess the mechanical and workability performance of mortar specimens with varying particle sizes of the TP as complete replacements for FA or SF. Microscopic analysis techniques, including X-ray diffraction (XRD), differential thermal analysis (DTG), and energy-dispersive X-ray spectroscopy (EDS), were employed to elucidate the hydration mechanism of the TP and its feasibility as a substitute for SF or FA. Results indicated that TP primarily functions as nuclei and filler, promoting cement hydration, with smaller particle sizes amplifying the hydration ability and increasing Ca(OH)2 and C-S-H gel content. The specimens with TP (median particle size 7.58 μm) demonstrated 9.2% and 29.9% higher flexural and compressive strengths at 28 days, respectively, compared to the FA specimens of equal mass. However, fluidity decreased by 23.1% accordingly. Due to TP’s smaller specific surface area compared to SF, the TP specimens exhibited higher fluidity but with decreased strength relative to the SF specimens. Overall, TP shows potential as a replacement for FA with additional measures to ensure workability.