<p>As a populous province and a major source of population outmigration, Anhui’s unique demographic and economic conditions impose strict requirements on the coordinated development of its population, economy, and environment, while also presenting significant challenges to the integration process of the Yangtze River Delta (YRD). Examining the current status of the coupling and coordination between population-economy-environment (PEE) systems can provide crucial insights for achieving high-quality development (HQD) in Anhui province in the new era. Using population census data and economic and environmental statistics from Anhui province (2000–2020), this study develops evaluation systems for PEE. The coupling degree model is employed to analyze trends and characteristics in the coupling and coordination among these systems. We found that (1) The development indices for population, economy, and environment across various cities exhibit significant internal variation, generally following a pattern of Southern Anhui &gt; Central Anhui &gt; Northern Anhui. (2) Coupling dominates in both population-economy (PECO) and population and environment (PENV) systems, though there is an increasing trend of cities displaying non-coupling features. Coordination is key in the PECO while non-coupling is more prominent in the PENV. (3) In the population, economy, and environment system, the Southern Anhui shows the highest degree of alignment and coupling among the three systems. The Central Anhui follows in terms of coupling and coordination, while the Northern Anhui exhibits the lowest due to significant constraints across all three factors, with the economy being the most limiting. This study proposes differentiated urban development strategies and policy insights for Anhui Province, offering a solid foundation to support its high-quality development and deeper integration into the YRD.</p>