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A surface plasmon resonance (SPR) sensor based on exposed‐core microstructured optical fibres (EC‐MOFs) is presented and numerically characterised. The exposed section (analyte channel) of the EC‐MOF is coated with a SPR supporting thin film of gold. The asymmetrically coated fibre can support two separate resonance peaks, with orthogonal polarisations (x‐ and y‐polarised peaks). Although the sensitivity of both the polarised peaks is very similar, the narrower linewidth of the y‐polarised peak provides a much enhanced signal‐to‐noise ratio. The SPR sensing performance for a large refractive index (RI) range from 1.33 to 1.42 is evaluated. The sensor has higher sensitivity for detecting the high analyte RI. The feasibility of using EC‐MOFs to develop a fast‐response, real‐time and distributed SPR sensor is determined. [ABSTRACT FROM AUTHOR]