The invention discloses a nanoliter spray -FTICR-MS analysis method and device for organic matters dissolved in an environmental solid sample. The device comprises a nanoliter spray device and a Fourier transform ion cyclotron resonance mass spectrum, wherein the nano-liter spraying device comprises a glass spray head, a conductive needle, a switching rubber head, a duplex pressurizing ball and a gas storage bag, a sample solution loaded by the glass spray head is a mixed solution consisting of interstitial water and an organic solvent, and a nozzle is aligned with a sample inlet of the Fourier transform ion cyclotron resonance mass spectrum. The nano-liter spraying device and the FTICR-MS are combined for use, a sample is purified and enriched through solid-phase extraction, the ionization efficiency is improved and ion selectivity inhibition is reduced by changing the formula of a matrix and nano-liter spraying, direct analysis of interstitial water in an environmental solid sample can be realized, and the key problems that in the prior art, bioactive molecule signals need to be lost through solid-phase extraction pretreatment, and common electrospray source selective signal inhibition is needed are solved.