The Stark effect on the R-q(22)(0,0.5) (nu=17 682.9251 cm(-1)) and P-q(11)(0,1.5) (nu = 17 682.1966 cm(-1)) branch features of the (0,0) B (2)A(1)-X (2)A(1) band system of calcium methoxide, CaOCH3, was measured and analyzed to give the magnitude of the permanent electronic dipole moments, \mu\, of 1.58(8) D and 1.21(5) D for the X (2)A(1) and B (2)A(1) states, respectively. The dipole moments are compared with other monovalent calcium compounds and those predicted from a simple electrostatic model. Pure rotational transitions in the X (2)A(1) state were recorded using the pump/probe microwave-optical double resonance technique. The proton magnetic hyperfine splitting pattern confirms a C-3v symmetry of the ground electronic state. The determined Fermi contact and dipolar parameters are: a(F)=-0.421(27) MHz; T-aa=1.070(45) MHz, and \T-bb - T-cc\=0.292(47) MHz. The latter parameter is associated with the lifting of the K-degeneracy of this symmetric top molecule and mixing the I-0=1/2 and I-0=3/2 levels.