This research details the characterisation of four Irish-grown lignocellulosic biomasses for pyrolysis by biomass composition analysis, TGA, and Py-GC/MS-FID. Ash content (mf) increased in the order spruce (0.26 wt.%) < salix (1.16 wt.%) < miscanthus (3.43 wt.%) < wheat straw (3.76 wt.%). Analysis of hydrolysis-derived sugar monomers showed that xylose concentrations (4.69–26.76 wt.%) ranged significantly compared to glucose concentrations (40.98–49.82 wt.%). Higher hemicellulose and ash contents probably increased non-volatile matter, and decreased the temperature of maximum degradation by TGA as well as yields of GC-detectable compounds by Py-GC/MS-FID. Differences in composition and degradation were reflected in the pyrolysate composition by lower quantities of sugars (principally levoglucosan), pyrans, and furans for salix, miscanthus, and wheat straw compared to spruce, and increased concentrations of cyclopentenones and acids.