•Graphene and graphene oxide were coated separately to the segmented SPME fibers.•The method allows a rapid, sensitive and simultaneous analysis of TCA and DBP in wines.•The method could be used for other contaminants with different volatilities in beverage.A novel space-resolved solid phase microextraction (SR-SPME) technique was developed to facilitate simultaneously analyte monitoring within heterogeneous samples. Graphene (G) and graphene oxide (GO) were coated separately to the segmented fibers which were successfully used for the solid-phase microextraction of two contaminants with dramatically different volatility: 2,4,6-trichloroanisole (TCA) and dibutyl phthalate (DBP). The space-resolved fiber showed good precision (5.4%, 6.8%), low detection limits (0.3 ng/L, 0.3 ng/L), and wide linearity (1.0–250.0 ng/L, 1.0–250.0 ng/L) under the optimized conditions for TCA and DBP, respectively. The method was applied to simultaneous analysis of the two contaminates with satisfactory recoveries, which were 96.96% and 98.20% for wine samples.