Pool fires are known to undergo a bifurcation to a globally unstable puffing state driven by baroclinic and buoyant vorticity production. Although the supercritical puffing regime away from the bifurcation has been studied extensively in the literature, no detailed account has been given of the critical conditions for its onset, that being the purpose of the present paper. For the relevant canonical case of round liquid pools without swirl, aside from the inherent thermochemical and transport parameters associated with the fuel, pool-fire puffing is governed by a single dimensionless number, the Rayleigh number, which scales with the cube of the pool diameter. Consequently, for a fixed fuel and under fixed ambient conditions, there is a critical fuel pool diameter, associated with a critical value of the Rayleigh number, above which the flame starts puffing. A global linear stability analysis that accounts for the axisymmetry of the prevailing instability mode is developed here to describe the bifurcation. The mathematical formulation employs the limit of infinitely fast reaction, with account taken of the nonunity Lewis number and vaporization characteristics of typical liquid fuels. Predictions of critical puffing conditions, including critical diameters and puffing frequencies, are provided for methanol and for heptane pool fires, and the results are compared with results of new small-scale experiments under controlled laboratory conditions, reported here, yielding reasonably good agreement. (C) 2018 The Combustion Institute. Published by Elsevier Inc. All rights reserved.