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The Hobomok Skipper (Poanes hobomok) is the only other skipper that shares the large, brown-bordered yellowish patch on the hindwing underside; in Peck's, this patch is separated into two areas by a median dark patch, and in Hobomok the pale patch is continuous throughout the median area. Males of these two species can also be separated by the presence of the prominent black dash on the forewing of P. peckius.

The description of the immature stages is summarized by Guppy & Sheppard (2001) as follows: The egg is pale green and round, mature larvae are dark maroon with light mottling and covered in dark hairs. This is presumed to be the overwintering stage. The reddish purple pupa is formed in a loose cocoon made within a bent blade of grass. It is generally considered to be a prairie / parkland species in the prairie provinces (Hooper 1973, Bird et al. 1995), but it also occurs locally in sedge marshes of the boreal forest north to at least La Butte Creek on the Slave River (Macaulay & Pohl 2002). Peck's Skipper also colonizes man-made, grassy habitats in the northern boreal parts of its range (Hooper 1973, Layberry et al. 1998).