Hemp is used as a source of fiber, oil and bioactive substances including volatile and cannabinoid-containing substances. This paper presents, for the first time, results on the evaluation of drying methods (convective, vacuum–microwave and combined convective pre-drying and vacuum–microwave finishing drying) of hemp leaves on the qualitative and quantitative changes in secondary metabolites, including essential oils, cannabinoids and sterols. A ranking and descriptive test of hemp leaves was also performed. Drying kinetics was presented using three models, including logarithmic, Midilli and modified Page. The SPME-Arrow technique was used to determine 41 volatile compounds, of which caryophyllene, β-myrcene and α-humulene were dominant in dried and fresh leaves. Regarding the essential oils obtained, 64 were identified, with caryophyllene, humulene epoxide II and limonene being the dominant ones. For preserving the highest amount of oils, the best method was the convective pre-drying followed by vacuum–microwave finishing drying (CD60-VMD) combined method, where the retention of volatile compounds was 36.08%, whereas the CD70 and 240-VMD methods resulted in the highest loss of 83%. The predominant cannabinoids in fresh hemp leaves were CBDA 6.05 and CBD 2.19 mg g−1. Drying caused no change in the cannabinoid profile of the plant material. β-Sitosterol, campesterol and lupeol were dominant in the phytosterol and triterpene fractions. No changes in either quality or quantity were observed in any of the variants found.