A 2 × 6 factorial experiment was conducted to determine the influences of dietary metabolizable energy (ME) and methionine (Met) levels on growth performance, carcass traits, and plasma biochemical parameters of starter Pekin ducks from 1 to 21 days of age. A total of 600 one-day-old male Pekin ducklings were randomly assigned to 12 groups (six replicates each group and eight ducks per replicate) in a 2 × 6 two-factor arrangement. The basal Met levels of two basal diets (11.54 and 12.52 MJ/kg ME) were 0.31 and 0.29%, respectively. The crystalline L-Met was supplemented to yield six diets according to different supplemental levels (0, 0.05, 0.10, 0.15, 0.20, and 0.25%). The results showed that the body weight (BW) and average daily weight gain (ADG) were increased (p < 0.05) with increasing dietary Met levels. Dietary ME levels changed from 11.54 to 12.52 MJ/kg increased the BW and ADG (p < 0.05) as well as decreased the average daily feed intake and feed to gain ratio (p < 0.05). As the dietary Met level increased, leg muscle yield increased (p < 0.05). Conversely, increasing the dietary ME level decreased the leg muscle yield (p = 0.0024) and increased abdominal fat (p < 0.001). Meanwhile, the concentrations of total cholesterol (TCHO), high-density lipoprotein cholesterol (HDLC), and low-density lipoprotein cholesterol (LDLC) in plasma were decreased (p < 0.05) when the ME levels of diets changed from 11.54 to 12.52 MJ/kg. Meanwhile, the plasma TCHO and HDLC concentrations decreased (p < 0.05) as dietary Met levels increased. Based on the linear-broken line model, the dietary Met requirement of starter Pekin ducks from 1 to 21 days of age for optimal ADG were 0.362% (0.052% supplemental L-Met) at 11.54 MJ ME/kg and 0.468% (0.178% supplemental L-Met) at 12.52 MJ ME/kg, respectively, when crystal L-Met was supplemented to formulate the diets. This suggested that the Met requirement of starter Pekin ducks was affected by dietary ME levels. The data potentially provide theoretical support for the utilization of crystalline L-Met in duck production.