The need to have a high-temperature adhesive that can withstand temperatures in excess of 350°C for MCM-D silicon substrate process application, yet which can be reworkable at slightly high temperature ϳ 400°C for the removal from the glass pallet, is important. A novel, reworkable, high-temperature adhesive based on polyimide-amide-epoxy (PIAE) copolymer was developed and investigated using modulated differential scanning calorimetry (MDSC), thermal gravimetric analysis (TGA), Fourier Transform Infrared Spectroscopy (FTIR) and solid-probe pyrolysis mass spectroscopy (MS). Compared with commercial polyimide-amide (PIA) adhesives, FTIR spectra reveal that the thermally degradative ester groups contribute to the reworkability of the PIAE adhesive at a specific temperature (400°C), yet they remain thermally stable at a lower working temperature (350°C). FTIR spectrum comparison of the residuals of PIAE and PIA are similar after exposure to 400°C. MS spectra of outgassed products identify that the components of radical fragmentation from PIAE are due to polymeric chain degradation at 400°C, while only volatile trace water and N-methyl pyrolidone (NMP) are evolved from the commercial PIA adhesive. TGA results suggest a complementary explanation for the variation of total ion current (TIC) curves on these two adhesives. MDSC curves further verify that the reworkable PIAE adhesive is a copolymer. Furthermore, a reasonable thermal degradation mechanism is presented on the adhesive reworkability.