This study focuses on microwave-assisted pyrolysis (MAP) of fresh waste tea powder and torrefied waste tea powder as feedstocks. Solvents including benzene, acetone, and ethanol were used for soaking feedstocks. The feedstock torrefaction temperature (at 150 °C) and solvents soaking enhanced the yields of char (44.2–59.8 wt%) and the oil (39.8–45.3 wt%) in MAP. Co-pyrolysis synergy induced an increase in the yield of gaseous products (4.7–20.1 wt%). The average heating rate varied in the range of 5–25 °C/min. The energy consumption in MAP of torrefied feedstock (1386 KJ) significantly decreased compared to fresh (3114 KJ). The pyrolysis index dramatically varied with the solvent soaking in the following order: ethanol (26.7) > benzene (25.6) > no solvent (10) > acetone (6). It shows that solvent soaking plays an important role in the pyrolysis process. The obtained bio-oil was composed of mono-aromatics, poly-aromatics, and oxygenated compounds.