The various Ni(I) species formed by thermal reduction and by hydrogen reduction in Ni(II)-exchanged silicoaluminophosphate-5 (NiH-SAPO-5) were studied by electron spin resonance and electron spin echo modulation spectroscopies. Four distinct Ni(I) species are observed in NiH-SAPO-5 heated to 873 K under vacuum : Ni(I)(O-z)(m)(H2O)(2) at room temperature where O-z is a zeolitic framework oxygen, Ni(I)(O-2)(n) between room temperature and 473 K, Ni(I)(O-z)(3) near the center of a 6-ring window (site SII) at temperatures between 473 K and 573 K, and Ni(I)(O-z)(6) inside a hexagonal prism (site SI) at temperatures above 773 K. Nickel metal clusters Ni(O)(n) are also observed by thermal reduction above 673 K. Two distinct Ni(I) species are observed in NiH-SAPO-5 after hydrogen reduction at 573 K : Ni(I)(O-z)(6) at site SI and Ni(I)(H-2)(n). A Ni(I)(O-2)(n) species is produced in NiH-SAPO-5 after hydrogen reduction, evacuation, and adsorption of water, indicating water decomposition. On adsorption of methanol, Ni(I) in site SI migrates near a 6-ring window and directly coordinates to two methanol molecules and indirectly to one methanol molecule at a greater distance. Ni(I) coordinates to one ethylene by a pi-bonding interaction.