In this study, the reliability performance of two capillary-type underfill materials with different glass transition temperatures (Tg) and coefficients of thermal expansion (CTE) were assessed for a chip stacking architecture. The microbumps for integrating four chips on a Si interposer were with a pitch size of 20 μm and composed of 5 μm Cu/3 μm Ni/5 μm Sn2.5Ag solder cap. A thermocompressive bonder was used to interconnect the microbumps at 280 °C for 15 s, and the microgaps between the chips and the interposer were then, respectively, sealed by the mentioned underfill materials to form a chip stacking architecture. Then, the reliability characteristics of the test vehicles were evaluated following the preconditioning and temperature cycling test (TCT). Furthermore, a numerical analysis model was established by ansys software to study the stress and strain contours of the microjoints sealed by different underfill materials. It was found that the lifetime of microjoints was highly related to the Tg points of underfills, an interfacial fracture was observed within the microjoints sealed by a lower Tg underfill after temperature cycling because the tensile strength damaged the Sn depletion zone as heated.