Leaf pigment concentrations are indicative of a range of plant physiological properties and processes. The measurement of leaf spectral reflectance is a rapid, non-destructive method for determining pigment content, and a large number of spectral indices have been developed for the estimation of leaf pigment content. Despite their 'applicability' across many species types, some ecologically important species remain to be explored. The objective of this paper was to investigate a wide range of hyperspectral indices for determining the chlorophyll and carotenoid content in a microphyllous and sclerophyllous species, Calluna vulgaris. We carried out spectral measurements on individual heather shoots with a handheld GER-1500 spectroradiometer, and sampled each measured shoot for biochemical analysis using high-performance liquid chromatography (HPLC). We found that several previously published indices performed relatively poorly and yielded coefficients of determination (R2) for chlorophyll ranging from 0.34 to 0.66, with the first derivative of reflectance at the red edge yielding the highest correlation with chlorophyll content (R2 = 0.66). Only one of the carotenoid indices we tested (the Photochemical Reflectance Index, PRI) provided a strong correlation with the de-epoxidation state of the xanthophyll cycle (R2 = 0.78). The other previously published carotenoid indices performed poorly within our data set. We concluded that only a few of the so-called 'widely applicable' indices were applicable to use with this data set, which would present limitations when working with remotely sensed data at a larger scale where a mix of species, including Calluna vulgaris, is present.