The chemical structure of neutral clouds in low-metallicity environments is examined, with particular emphasis on the H to H-2 and C+ to CO transitions. We observed near-IR H-2 (1, 0) S(1), (2, 1) S(1), and (5, 3) 0(3) lines and the (CO)-C-12 J = 1 --> 0 line from 30 Doradus and N159/N160 in the Large Magellanic Cloud and from DEM S 16, DEM S 37, and LI-SMC 36 in the Small Magellanic Cloud. We find that the H, emission is UV-excited and that tweak) CO emission always exists tin our surveyed regions) toward positions where H-2 and [C II] emission have been detected. Using a PDR code and a radiative transfer code, we simulate the emission of line radiation from spherical clouds and from large planar clouds. Because [C II] emission and H-2 emission arise on the surface of the cloud and because the lines are optically thin, these lines are not affected by changes in the relative sizes of the neutral cloud and the GO-bearing core, while the optically thick CO emission can be strongly affected. The sizes of clouds are estimated by measuring the deviation of CO emission strength from that predicted by a planar cloud model of a given size. The average cloud column density, and therefore its size, increases as the metallicity decreases. Our result agrees with the photoionization-regulated star formation theory of McKee.