The reliability of structural systems has to be verified against failure caused by extreme effects, such as fire and seismic effects. To the best of the authors' knowledge, there is a lack of studies in the literature on comprehensive reliability calculation of complex structural systems; the available studies mainly deal with the reliability calculation of simple, separated elements. In this study, a methodology is presented for the calculation of reliability of structures under fire exposure, giving a more complex and comprehensive basis for the calculation of structural reliability than earlier studies in the literature: a) the reliability calculation does not focuses on one single element but the whole structure; b) the presented methodology is able to consider any type of fire curve; c) reliability analysis includes the nonlinear analysis of the structure, in this way the highly nonlinear structural response is followed; d) the structural reliability is assessed on time basis. The applicability of the proposed algorithm is presented through reliability calculation of tapered portal frame structure protected by intumescent coating, as an example structure. The probability of failure is calculated using First Order Reliability Method. The resulted probabilities are verified using Monte Carlo Simulation.