Alkaloids constitute a structurally heterogeneous group of nitrogenous secondary metabolites with widespread distribution in fungi and plants, and numerous members of this group are bioactive and of pharmacological interest. Conventional extraction techniques, like acid-base fractionation, have been traditional starting reagents but are plagued by key drawbacks in the form of the use of harmful solvents, low selectivity, degradation of the analytes, and high environmental load. Advances in green chemistry and extraction methodology over the recent past have helped usher in more efficient and eco-friendly alternatives. This chapter examines both traditional and novel alkaloid extraction approaches and highlights two contrasting processes. The first utilizes ultrasound-assisted complete extraction with an ionic liquid non-aqueous solvent system (UACE-ILNAS) to extract isoquinoline alkaloids from Phellodendron amurense. The combination of the ionic liquid [C4mim][OAc] with DMSO delivers improved penetration through lignified plant material and high yields, improving viscosity and waste solvent reduction. The second protocol describes a conventional methanol-extraction of indole and oxindole alkaloids from Mitragyna speciosa (kratom). The protocol involves argon-assisted methanol reflux, acid-base manipulation, solvent partitioning, and column chromatography to extract both major and minor alkaloids such as mitragynine and isopaynantheine. Collectively, these methods demonstrate how the integration of traditional principles and contemporary advances can enhance efficiency, lessen environmental footprint, and facilitate the isolation of pharmacologically active alkaloids from otherwise difficult-to-handle plant matrices.