To explore the effects of the degree of polymerization of polyvinyl alcohol (PVA) as a binder, the content of boronic acid (HB) as a crosslinking agent, polyaniline (PANI) and chitosan (CTS) as an additive on the mechanical properties and combustion start-stop performance of hydroxylamine nitrate based electrically controlled solid propellants (HAN-ECSP), the samples were prepared by the swelling method. The mechanical properties and combustion start-stop performance were studied by tensile test, combustion start-stop performance test, X-ray diffraction (XRD), Fourier transform infrared attenuated total reflection (FTIR-ATR), and optical electron microscopy. The findings indicate that there is minimal variation in crystallinity among PVA samples with different degrees of polymerization. But when the polymerization degree of PVA is 2400±50, the ─OH content is relatively high and the mechanical properties are better. The HB content influences the crosslinking density of PVA. PVA2499-20% HB exhibits a relatively low density and uneven surface depressions. PVA2499-18% HB demonstrates superior mechanical properties, boasting a tensile strength of 2.36 MPa and a tensile elongation of 482.92%. However, it is highly corrosive to the copper electrode. Therefore, an initial network is formed by cross-linking 8% HB with PVA. The PANI or CTS is added to form a semi-interpenetrating polymer network with PVA. The tensile strength of the PVA2499-8% HB-2% PANI propellant is 1.03 MPa, and its elongation at break is 432.85%. The tensile strength of the PVA2499-8% HB-1% CTS propellant is 0.87 MPa, and its elongation at break is 302.28%. Both PANI and CTS addition to the ECSP can achieve start-stop, and the maximum burning temperature can reach 800 ℃.