The zeros of the canonical partition functions for flexible square-well polymer chains have been approximately computed for chains up to length 256 for a range of square-well diameters. We have previously shown that such chain molecules can undergo a coil-globule and globule-crystal transition as well as a direct coil-crystal transition. Here we show that each of these transitions has a well-defined signature in the complex-plane map of the partition function zeros. The freezing transitions are characterized by nearly circular rings of uniformly spaced roots, indicative of a discontinuous transition. The collapse transition is signaled by the appearance of an elliptical horseshoe segment of roots that pinches down towards the positive real axis and defines a boundary to a root-free region of the complex plane. With increasing chain length, the root density on the circular ring and in the space adjacent to the elliptical boundary increases and the leading roots move towards the positive real axis. For finite-length chains, transition temperatures can be obtained by locating the intersection of the ellipse and/or circle of roots with the positive real axis. A finite-size scaling analysis is used to obtain transition temperatures in the long-chain (thermodynamic) limit. The collapse transition is characterized by crossover and specific-heat exponents of φ≈0.76(2) and α≈0.66(2), respectively, consistent with a second-order phase transition.