The final form of tubular nanofibres produced by the co-electrospinning of two solutions (core/shell) is largely determined by the kinetics governing the buckling phenomenon. The buckling mechanism involves the evaporation of the core solution through a solidified shell resulting in a pressure difference across the fibre shell. Buckling can take place when the pressure drop across the fibre shell exceeds a critical value. In this work the physical conditions leading to fibre buckling are analysed from a kinetic point of view. A time interval, Delta t, during which buckling may occur, is introduced as a single criterion determining the buckling probability. Different core/shell systems were spun by varying the surface tension, viscosity, flow rate, electric field and the diffusion coefficient of the core solvent through the fibre shell. The imaged as-spun nanofibres were analysed statistically to determine the buckling probability, and the corresponding Delta t values were calculated using the values of the spinning parameters. The obtained data were fitted with an exponential distribution function which afforded determination of the characteristic time to buckling, t(b). The results provide a means of predicting the buckling of tubular nanofibres. In particular, one can conclude that the dominant parameter determining the final form of the as-spun tubular nanofibres is the diffusion coefficient of the core solvent through the fibre shell.