The present work reports a comparative analysis of natural convection heat transfer from a thick hollow vertical cylinder either placed on the ground or suspended in the air. The numerical simulations have been performed by varying the cylinder length to its outer diameter (L/Do) in the range of 0.2–20, the thickness ratio (Di/Do) in a range of 0.5–0.9, and Rayleigh number (Ra) from 104 to 108. The flow and heat transfer characteristics have been delineated precisely with the presentation of the thermal plume and flow field in the vicinity of the cylinder. The variation of average Nusselt number (Nu), local Nu, and contribution to total heat loss from different surfaces with the pertinent parameters have been elucidated graphically. The average Nu is always more for the cylinder in the air compared with the case when it is on the ground. However, the difference between the Nu for these two cases diminishes, as the L/Do increases. It has also been found that the contribution to total heat loss from the inner surface of the hollow cylinder suspended in air increases with L/Do, attains a peak, and decreases sharply. Cooling time curves for the cylinder placed in air or on the ground have been described precisely. Finally, a correlation for the average Nusselt number as a function of all the pertinent parameters has been proposed that can be useful for industrial and academic purposes.