A π-conjugated polymer containing spiropyrans (SPs), which could be almost completely converted to protonated merocyanines (MCH+) and back to the SP form by adding an acid and a base, respectively, was developed. The insulation of the π-conjugated polymer, referred to as insulated spiropyran-containing poly(p-phenylene ethynylene) (ins-SP-PPE), using permethylated α-cyclodextrins (PM α-CD) suppressed the π-π interaction between the polymer chains containing MCH+, and the installation of PM α-CD improved the switching ability of SPs. The polymer exhibited repeatable acidochromism with almost complete conversion between the SP and MCH+ forms. Photoluminescence measurements were conducted and the acid-induced luminescence quenching of the polymer in the solution was observed, which stemmed from energy transfer from the PPE to MCH+ moieties. In the solid state, the quantum yield of ins-SP-PPE was more than twice that of the uninsulated polymer, which derived from the insulation effects. The acid-induced luminescence quenching was also observed in the solid state.