Yes, it is possible to sync person accounts with HubSpot, though there are some things to keep in mind.
What is a Person Account?
Salesforce accounts are business accounts by default. Business accounts are used to store information about companies or other entities and sync with HubSpot companies. Salesforce administrators can also choose to set up person accounts which are used to store information about individual people.
Person accounts operate slightly differently than business accounts in that they cannot have associated contacts. Instead, they use a particular record type ID to store both an account and contact on the same layout. It is necessary to reach out to Salesforce Support to enable person accounts and important to make sure these preliminary steps have been taken prior to enabling in Salesforce.
Syncing Person Accounts with HubSpot
When you create a person account, Salesforce creates not only an account but a contact in the background. While the contact is not directly visible in Salesforce, this is why HubSpot creates a unique company and contact record when Person Accounts are enabled (when auto-add and Account sync are enabled).
If you have chosen the setting to create Salesforce contacts when a contact is created in HubSpot, a standard contact record will be created which may be associated with a Salesforce business account, but not a person account.
Currently HubSpot cannot create person accounts. You can, however, set the integration to create leads in Salesforce when new contacts are created in HubSpot (Account Menu > Integrations > Settings under Salesforce > Creating Records in Salesforce: Default Object).
With this setting enabled, once the lead is created you may convert them to a person account as long as the lead does not already have the ‘Company’ property populated on the Lead record. Leads that already have a value in the company field are converted to business account instead. Learn more about this here.