From Lophophora williamsii var. caespitosa, pellotine, anhalidine, anhalonidine, and anhalamine were obtained as phenolic alkaloids, and lophophorine was isolated as a nonphenolic alkaloid, which all belong to the tetrahydroisoquinoline system. A kind of betaine-type yellow components, anhalotine (=Y₁=I), Y₂ (II), Y₃ (III), and peyotine (=Y₄=IV) were isolated. They were the derivatives of 6, 7-dimethoxy-3, 4-dihydro-8-hydroxy isoquinolinium innersalt. Similar types of tautomerism were found in I and IV, and they had pKa 6.0 and 6.5, respectively. Another type of tautomerism was found in II and III. II had pKa₁ 5.6 and pKa₂ 10.9, and III had pKa₁ 6.7 and pKa₂ 11.4.