This paper presents an efficiency evaluation of GC coupled with quadrupole Orbitrap MS for identification and quantitation in the multiresidue pesticide analysis of baby foods in full-scan mode. The identification criteria were studied following SANTE guidelines (retention time, mass accuracy, and ion ratio), comfortably complying with the values established, even at 0.003 mg/kg. Method validation was carried out on 15 selected GC-amenable pesticides covered by Commission Directive No. 2006/125/EC in three different baby food matrixes. Recovery studies were performed at 0.003 and 0.006 mg/kg, with 96% of the cases falling within the 70-120% range and with RSDs <15% for all the pesticides assayed. Linearity over 3 orders of magnitude was verified, with residuals <16% and correlation coefficient values >0.995. In general, matrix effect values were >100%. The LOQ was 0.003 mg/kg for 97% of the cases. The validated method was applied to 20 real baby food samples from Spain and to the European Union Proficiency Test FV-BF01 sample, in which the z-scores obtained were <1, thus demonstrating that this instrumentation has good quantitation capabilities.