Best solvent for extracting psilocybin, psilocin, and baeocystin is pure methanol, it does not have to be anhydrous.

Then you evaporate, dissolve in dilute acetic acid and wash with chloroform to remove any non-alkaloid organics. Then to recrystallize, basify with bicarbonate, extract with chlorofom, evaporate, subject to HPLC for analysis.

The result of this process is a freebase oil that would need to be recrystallized if crystals / solid were desirable.

Psilocybin/psilocin are not soluble in chloroform when in acidic solution because they are alkaloids and are (+) charged in acids and neutral in bases and are thus soluble in water when acidic and soluble in non-polar solvents when neutral in a basic solution.

A good recrystallization solvent for psilocybin is superheated water.

See Gartz 1994.