The photochemistry of isomeric methoxyphenyl chlorides and phosphates has been examined in different solvents (and in the presence of benzene) and found to involve the triplet state. With the chlorides, C-Cl bond homolysis occurs in cyclohexane and is superseded by heterolysis in polar media, while the phosphate group is detached (heterolytically) only in polar solvents. Under such conditions, the isomeric triplet methoxyphenyl cations are the first formed intermediates from both precursors, but intersystem crossing (isc) to the singlets can take place. Solvent addition (forming the acetanilide in MeCN, the ethers in alcohols, overall a S(N)1 solvolysis) is a diagnostic reaction for the singlet cation, as reduction and trapping by benzene are for the corresponding triplet. Solvolysis is most important with the meta isomer, for which the singlet is calculated (UB3LYP/6-31g(d)) to be the ground state of the cation (Delta E = 4 kcal/mol) and isc is efficient (k(isc) ca. 1 x 10(8) s(-1)), and occurs to some extent with the para isomer (isoenergetic spin states, k(isc) ca. 1.7 x 10(6) s(-1)). The triplet is the ground state with the ortho isomer, and in that case isc does not compete, although trapping by benzene is slow because of the hindering of C-1 by the substituent. The position of the substituent thus determines the energetic order of the cation spin states, in particular through the selective stabilization of the singlet by the m-methoxy group, a novel case of "meta effect".