The effect of sodium formate (SF), calcium formate (CF) and nickel formate (NF) as additives on analytical pyrolysis performance of kraft lignin was conducted. The results showed that these formates promoted the releasing of volatiles, leading to the rapid degradation of kraft lignin. High relative content of monophenols (53.77%), especially of guaiacol (23.65%), were achieved from the pyrolysis of pure lignin. The relative content of guaiacol was dramatically decreased after the adding of formates in kraft lignin. The relative content of polyphenols such as 3-methylcatechol and 4-methylcatechol reached to 16.97%, 16.23% and 21.95% with the formates of SF, CF and NF, respectively. The NF showed the highest selectivity of polyphenols and hydrocarbons. The increase of polyphenols and hydrocarbons from NF was the synergetic effect of the hydrogen radical reaction from the formic functional groups under the catalysis of Ni and/or NiO produced from the NF pyrolysis process.