An automated, confirmatory and sensitive procedure has been developed and validated for the determination of Sudan (I-IV), Sudan Orange G, Sudan Red 7B and Para Red in hot chilli food samples. The proposed method includes pressurised liquid extraction (PLE) with acetone, gel permeation chromatography (GPC) clean-up and detection by liquid chromatography (LC) coupled to electrospray ionization in positive mode tandem mass spectrometry (ESI-MS-MS). The main parameters affecting the performance of the different ionization sources and PLE parameters were previously optimised using statistical design of experiments (DOE). The method was in-house validated on chilli powder and chilli meat. Linear calibrations were obtained with correlation coefficients R(2)>0.999. The limits of detection (LOD) and quantification (LOQ) of the method were in the ranges of 0.002-0.012 ng g(-1) and 0.006-0.036 ng g(-1), respectively for chilli powder. The decision limit and detection capability were between 0.005-0.022 ng g(-1) and 0.007-0.026 ng g(-1), respectively for chilli meat. Recoveries ranged from 94% to 105%. The applicability of the method to the determination of azo-dyes in hot chilli products was demonstrated.