Kinetic studies on the reactions of Y-S-aryl phenyl phosphonochloridothioates with X-pyridines have been carried out in MeCN at $55.0^{circ}C$. The Hammett and Bronsted plots for substituent X variations in the nucleophiles are biphasic concave upwards with a break point at X = H. The Hammett plots for substituent Y variations in the substrates are biphasic concave upwards with a break point at Y = H, and the sign of ${ ho}_Y$ is changed from unusual negative (${ ho}_Y$ < 0) with the weaker electrophiles to positive (${ ho}_Y$ > 0) with the stronger electrophiles. The stepwise mechanism is proposed on the basis of the ${ ho}_X$, ${eta}_X$, and ${ ho}_{XY}$ values as follows: a ratelimiting leaving group departure from the intermediate involving a frontside attack and product-like TS for the stronger nucleophiles and weaker electrophiles; a rate-limiting leaving group departure from the intermediate involving a backside attack and product-like TS for the weaker nucleophiles and electrophiles; a rate-limiting bond formation involving a frontside attack for the stronger nucleophiles and electrophiles; a rate-limiting bond formation involving a backside attack for the weaker nucleophiles and stronger electrophiles. The substituent effects of X and Y on the pyridinolysis mechanisms of $R_1R_2P$(=S)Cl-type substrates are discussed.