This study reports the use of front-face fluorescence spectroscopy with principal component analysis (PCA) as a tool for the characterisation of selected Polish herbhoneys (raspberry, lemon balm, rose, mint, black current, instant coffee, pine, hawthorn, and nettle). Fluorimetric spectra registered in the ranges ascribed to fluorescence of amino acids, polyphenols, vitamins, and products of Maillard’s reaction enabled the comparison of herbhoney compositions. Obtained synchronous spectra combined with PCA were used to investigate potential differences between analysed samples and interactions between compounds present in them. The most substantial influence on the total variance had the intensities of polyphenols fluorescence. These intensities were the main factor differentiated by the analysed products.