Based on the panel data of 16 cities in Anhui from 2010–2018, this paper measures the index system of fiscal structure and high-quality economic development in Anhui using the entropy weight method, and empirically analyzes the coordinated development level of fiscal structure and high-quality economic development in Anhui using coupled coordination degree model. The study finds that: (1) the overall structure of Anhui’s fiscal expenditure is characterized by "service-oriented and investment-oriented", and there is a phenomenon that contradicts "Wagner Principle", and there are also spatial and temporal differences in Anhui’s tax structure. (2) The level of high-quality development of Anhui economy shows a steady upward trend, but is still at a low level. (3) The level of coordinated development of fiscal structure and high-quality economic development is still low, and the overall situation is "on the verge of disorder" or "barely coordinated". (4) Regionally, the overall coordination of fiscal expenditure structure, tax structure, and high-quality economic development in southern Anhui shows a decreasing trend, while the overall coordination in central and northern Anhui shows an increasing trend, so that southern Anhui has been or will be surpassed by northern and middle Anhui, and the growth rate of middle Anhui is faster than that of northern Anhui.