The invention relates to an ultra-thick high temperature-resistant steel for a pressure vessel and a preparation method thereof. After smelting and refining, the steel is subjected to continuous casting, hot rolling, normalizing and tempering. The steel comprises the following controlled chemical components in percentage by mass: 0.08-0.15% of C, 0.15-0.40% of Si, 0.40-0.70% of Mn, 0.90-1.20% of Cr, 0.15-0.30% of V, 0.25-0.35% of Mo, at most 0.025% of P, at most 0.010% of S and the balance of Fe and inevitable inclusions. The preparation method provided by the invention comprises the steps of smelting, heating, rough rolling, finish rolling, normalizing and tempering. The invention has the characteristics of appropriate design and proportion of the chemical components, simple manufacturing process, large thickness dimension (80mm), good heat resistance, stable product performance and the like.