A series of phenylacetoxy cellulosics with degrees of substitution (DS) between 1.4 and 3.0 and different halogenation (2-chloro, 3-chloro, 4-chloro, 2,4-dichloro, 3,4-dichloro, and 4-bromo) were synthesized. All the prepared phenylacetoxy cellulosics were soluble in dimethylformamide (DMF) and DMAc. The solubility increased with increasing DS. Mesophases were observed for all of the phenylacetoxy cellulosics with low to medium DS (DS<2.5) in DMF and DMAc. Non- or mono-halogeneated phenylacetoxy cellulosics with high DS (DS>1.9) were soluble in methylene chloride (CH2Cl2), whereas those with very low DS or di-halogenation on the phenyl ring were only slightly swollen or partially soluble in CH2Cl2. Non- and mono-halogenated phenylacetoxy cellulosics were soluble in DMSO and formed liquid crystals regardless of the DS, in contrast to CH2Cl2 solutions which display liquid crystalline behavior at medium to high DS (DS>1.9) only. The solubility of the di-halogenated phenylacetoxy cellulosics in DMSO was limited to similar to40 wt %.