Two molecules of tetra(4-pyridyl)cavitand 1 and four molecules of isophthalic acid linker 2a with a triethylene glycol monomethyl ether (TEG) group self-assembled into a six-component capsule 12·2a4 through eight pyNHO2C hydrogen bonds, which encapsulates one molecule of guest G such as bis(4-acetoxyphenyl)acetylene and hexakis(4-iodophenyl)benzene to form G@(12·2a4). Guest-encapsulation ability and selectivity of 12·2a4 were revealed. trans-5-(p-Substituted-phenylazo)isophthalic acid with two dichotomous branching TEG groups trans-2b serves as a photoresponsive linker to form 12·(trans-2b)4, which moderately reduced guest-encapsulation ability upon photoisomerization (at the photostationary state, 10% guest release upon subunit-trans-2b/subunit-cis-2b = 18 : 82).