Bamboo is a natural and renewable building material but its application has been limited due to the low dimensional stability and poor durability against mold. In this study, monomers of hydroxyethyl methacrylate (HEMA) and N-isopropyl acrylamide (NIPAM) were impregnated in bamboo to facilitate the in situ growth of poly-HEMA and NIPAM (PHN) copolymer. Prior to that, the effects of different reaction conditions, including the molar ratio of HEMA to NIPAM and their concentrations, the amount of initiator (ammonium persulfate, APS) and crosslinking agents (N,N′-Methylenebisacrylamide (MBA), and glutaric dialdehyde (GA)) on the swelling capacity of PHN were optimized. The formation of PHN was confirmed by using Fourier transform infrared spectroscopy and thermogravimetric analysis, which shows the characteristics peaks of both HEMA and NIPAM, and increased pyrolysis and glass transition temperatures, respectively. After impregnation of PHN pre-polymerization formulation to bamboo, it was observed that PHN filled most of the pits in the bamboo cell wall and formed a tight network. Moreover, the dimensional stability of PHN treated bamboo was significantly improved with an anti-swelling efficiency of 49.4% and 41.7%, respectively, after wetting–drying and soaking–drying cycles. A mold infection rate of 13.5% was observed in PHN-treated bamboo as compared to a 100% infected control group after a 30-day mold resistance test. Combined results indicate that in situ polymerization of HEMA and NIPAM in bamboo is a promising method to develop exterior used bamboo products with enhanced dimensional stability and mold resistance.