Shaping the canopy architecture and delaying leaf senescence in maize are pivotal strategies for extending the crop’s photosynthetic period and improving yield. The application of plant growth regulators (PGRs) is a critical cultivation measure, with the timing of application being of paramount importance. To explore the effects of PGR application time on maize canopy structure, leaf senescence characteristics and yield, a comparative two-year field study was undertaken during the 2019–2020 growing seasons at the Gongzhuling Experimental Station of the Jilin Academy of Agricultural Sciences, utilizing a PGR containing ethephon as the active ingredient. The experiment was structured with two plant densities of 60,000 and 90,000 plants ha−1, and three distinct PGR application protocols: T10 (application of PGR at the 10th leaf stage), T15 (application at the 15th leaf stage), and CK (control group sprayed with water). The result indicated that the yield increased by 5.62% following T15 treatment compared to the CK under high density (90,000 plants ha−1). Furthermore, the kernel per ear and the 1000-kernel weight increased by 3.93% and 5.62% respectively, while the abortion rate decreased. Correlation analysis showed that yield and yield components were correlated with plant morphology, physiology, and aging characteristics under 90,000 plants ha−1. Pollen density was also positively correlated with the top leaf area and the top leaf angle (p < 0.01). Furthermore, relative green leaf area at maturity (RGLAM) showed positive correlations with chlorophyll b, superoxide dismutase activity (SOD), peroxidase activity (POD), catalase activity (CAT), and soluble protein content (p < 0.01), while displaying a negative correlation with malondialdehyde content (MDA) (p < 0.01). Spraying plant growth regulators at the 15-leaf stage under high density can effectively enhance the top canopy structure of the maize and reduce the upper leaf area and angle, increase pollen density, and boost the number of grains. Furthermore, it delayed the senescence of leaves, prolonged the functional period of the leaves, increased kernel weight, optimized light resource utilization, and ultimately enhanced the maize yield.
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