This paper presents analyses of the thermophysical and chemical properties of eleven perennial crop species harvested in one-year rotation cycles. The crops included four species grown for biomass in the form of straw, five species producing semi-wood biomass, and two species yielding wood biomass. The research comprised three consecutive crop harvests. In each harvesting season, biomass samples for analyses were taken on six dates at one-month intervals. Thermophysical and chemical properties of the biomass were significantly differentiated within the main experimental factors and their interactions. The biomass produced by Virginia mallow had the best quality parameters as solid fuel. In fact, it achieved the lowest water content and the highest lower heating value during all of the analyzed seasons and harvest dates. The biomass of the species yielding straw or semi-wood products attained better quality as solid fuel on later harvest dates. In turn, the quality of willow biomass remained practically unchanged between the harvest dates.