A new series of chiral homologous thiobenzoates with non-chiral end chains ranging from heptyloxy to octadecyloxy has been synthesized and characterized. The mesomorphic properties have been analysed by optical microscopy on pure compounds and mixtures, DSC, and electro-optical and pitch measurements. They display a very rich polymesomorphism including SA, S*Cα, S*C, S*CFI, S*CAphases with reference to the compound MHPOBC through miscibility tests. Peculiarly noticeable are: (i) two S*CFIphases sandwiched between S*Cand S*CAphases in some compounds; (ii) full miscibility between the S*CAphase and the S*Ophase of the racemic reference compound MHTAC which leads us to question whether the S*CAor S*Osymbol should be used to designate the antiferroelectric smectic C* phase; (iii) odd-even cancellation of the S*CAphase in relation to both the chiral chain and the alkyloxy chain; (iv) a reentrant sequence, C SCSCASCSAI, in a pure compound assessed by a phase diagram. The electro-optical measurements were carried out with the classical SSFLC geometry. The field threshold is determined for each titled mesophase. One can note: (i) a low threshold whatever the phase; (ii) a first plateau at 0·4 Vμm−1and a saturation at 1 Vμm−1in the S*CFIphase; (iii) strong pretransitional variations of the pitch at the S*CA-S*CFIand S*CFI-S*Ctransitions.